N&#39;-(substituted-pyrimidin-2-yl)-N&#34;-amino-N&#34;&#39;-(substituted-benzenesulphonyl)-guanidines as herbicides

ABSTRACT

Herbicidally active guanidine derivatives of the formula ##STR1## in which m represents the numbers zero, 1 or 2, 
     R 5  represents an optionally substituted radical from the series comprising alkyl, aralkyl, aryl and heteroaryl, 
     R 2  represents a pyrimidin-2-yl radical which is substituted by halogen, amino, cyano or formyl and/or by optionally substituted radicals from the series comprising alkyl, alkoxy, alkylamino, dialkylamino, alkylcarbonyl and alkoxycarbonyl, 
     R 3  represents hydrogen, an optionally substituted radical from series comprising alkyl, cycloalkyl, alkenyl, alkinyl and aralkyl, 
     R 9  represents hydrogen or optionally substituted alkyl and 
     R 10  represents an optionally substituted radical from the series comprising alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aryl, heteroaryl, alkyl- or alkoxycarbonyl and alkyl- or arylsulphonyl, or R 9  and R 10  together represent alkanediyl which is optionally interrupted by an oxygen atom; and 
     M represents hydrogen, one equivalent of a metal, or an ammonium radical which is optionally substituted by alkyl, alkenyl, alkinyl and/or aralkyl, or--in the case in which M is bonded to the same nitrogen atom as R 2  --also represents an optionally substituted radical from the series comprising alkyl, alkenyl, alkinyl and aralkyl, 
     or acid adducts thereof.

This is a continuation-in-part of application Ser. No. 769,271 filedAug. 23, 1985, now pending, and of application Ser. No. 853,822, filedApr. 18, 1986, now pending, which is a division of application Ser. No.578,345, filed Feb. 9, 1984, now U.S. Pat. No. 4,602,938.

The invention relates to new guanidine derivatives, several processesfor their preparation and their use as herbicides and plant growthregulators.

Patent specifications (see, for example, DE-AS (German PublishedSpecification) No. 1,089,210 and East German Patent Specifications Nos.71,016 and 84,530) have disclosed that various guanidines are potentialherbicides, but these compounds have been relatively unimportanthitherto as agents for combating weeds and/or regulating plant growth.

New guanidine derivatives of the general formula (I) ##STR2## have beenfound, in which R¹ represents hydrogen or the radical --S(O)_(m) --R⁵,

wherein

m represents the numbers zero, 1 or 2 and

R⁵ represents an optionally substituted radical from the seriescomprising alkyl, aralkyl, aryl and heteroaryl,

R² represents a six-membered aromatic heterocyclic structure whichcontains at least one nitrogen atom and is substituted by halogen,amino, cyano or formyl and/or by optionally substituted radicals fromthe series comprising alkyl, alkoxy, alkylamino, dialkylamino,alkylcarbonyl and alkoxycarbonyl, and/or is optionally fused,

R³ represents hydrogen, an optionally substituted radical from theseries comprising alkyl, cycloalkyl, alkenyl, alkinyl and aralkyl, orthe radical --S(O)_(n) --R⁶,

wherein

n represents the numbers zero, 1 or 2 and

R⁶ represents an optionally substituted radical from the seriescomprising alkyl, aralkyl, aryl and heteroaryl,

R⁴ represents hydrogen or hydroxyl, with the proviso that then at leastone of the radicals R¹ and/or R³ is not hydrogen;

and in which furthermore--in the case in which R³ is not hydrogen--

R⁴ represents an optionally substituted radical from the seriescomprising alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl and aryl, or

R³ and R⁴ together represent alkanediyl which is optionally interruptedby an oxygen atom or by a bridge ##STR3## wherein R⁷ representsoptionally substituted alkyl, alkylcarbonyl or aryl;

and in which furthermore

R⁴ represents the radical --X--R⁸,

wherein

X represents oxygen, sulphur, --SO-- or --SO₂, and

R⁸ represents an optionally substituted radical from the seriescomprising C₁ -C₆ -alkyl, alkenyl, alkinyl, cycloalkyl, phenylalkyl andaryl,

and in which furthermore

R⁴ represents the radical ##STR4## wherein R⁹ represents hydrogen oroptionally substituted alkyl and

R¹⁰ represents an optionally substituted radical from the seriescomprising alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl, aryl,heteroaryl, alkyl- or alkoxycarbonyl and alkyl- or arylsulphonyl, or R⁹and R¹⁰ together represent alkanediyl which is optionally interrupted byan oxygen atom;

and in which furthermore

R⁴ represents the radical ##STR5## wherein R¹¹ represents hydrogen oroptionally substituted alkyl and

R¹² represents an optionally substituted radical from the seriescomprising alkyl, alkenyl, alkinyl, cycloalkyl, aralkyl and aryl or R¹¹and R¹² together represent alkanediyl,

and in which furthermore

R⁴ represents trialkylsilyl or the radical ##STR6## wherein q representsthe numbers zero or 1,

Y represents oxygen or sulphur and

R¹³ and R¹⁴ are identical or different and individually representoptionally substituted radicals from the series comprising alkyl,alkenyl, aralkyl, alkinyl, aryl, alkoxy, alkenoxy, alkinoxy, aralkoxy,aryloxy, alkylthio, alkenylthio, aralkylthio, alkinylthio, arylthio,amino, alkylamino and dialkylamino, or

R¹³ and R¹⁴ together represent alkanedioxy, oxyalkyleneamino oralkanediamino;

and in which furthermore

R⁴ represents an optionally substituted heterocyclic radical,

and in which furthermore

M represents hydrogen, one equivalent of a metal, or an ammonium radicalwhich is optionally substituted by alkyl, alkenyl, alkinyl and/oraralkyl, or--in the case in which M is bonded to the same nitrogen atomas R² --also represents an optionally substituted radical from theseries comprising alkyl, alkenyl, alkinyl and aralkyl.

Furthermore, new 1:1 adducts of compounds of the formula (I), wherein,in this case,

M represents hydrogen and

R¹, R², R³ and R⁴ have the meanings given above,

with strong acids have been found.

In the case in which M represents hydrogen, the new guanidinederivatives illustrated by the general formula (I) occur as mixtures oftautomers of the formulae (IA) and (IB): ##STR7## The ratio in themixture depends on aggregation-determining factors, such as, forexample, temperature, solvent and concentration.

In the case in which, in addition to M, R³ and/or R⁴ also representhydrogen, the general formula (I) also represents other possibletautomers, as illustrated in the formulae (IC) and (ID): ##STR8##

The new guanidine derivatives of the formula (I) are obtained

(a) in the case in which R¹ represents hydrogen, R³ represents hydrogenor an optionally substituted radical from the series comprising alkyl,cycloalkyl, alkenyl, alkinyl and aralkyl, M represents hydrogen or anoptionally substituted radical from the series comprising alkyl,alkenyl, alkinyl and aralkyl, and the radicals R² and R⁴ have themeanings given above, if cyano compounds of the formula (II) ##STR9## inwhich M¹ represents hydrogen or an optionally substituted radical fromthe series comprising alkyl, alkenyl, alkinyl and aralkyl and

R² has the meaning given above,

are reacted with amino compounds of the formula (III) ##STR10## in whichR³ represents hydrogen or an optionally substituted radical from theseries comprising alkyl, cycloalkyl, alkenyl, alkinyl and aralkyl, and

R⁴ has the meaning given above,

or with hydrochlorides of amino compounds of the formula (III), ifappropriate in the presence of diluents, and, if required, the reactionproducts are treated with acid acceptors; or

(b) in the case in which R¹ represents the radical --S(O)_(m) --R⁵,

wherein

m and R⁵ have the meanings given above, and M represents hydrogen or anoptionally substituted radical from the series comprising alkyl,alkenyl, alkinyl and aralkyl,

and wherein furthermore

the radicals R², R³ and R⁴ have the meanings given above, or in the casein which R³ represents the radical --S(O)_(n) --R⁶,

wherein

n and R⁶ has the meanings given above, and

M represents hydrogen or an optionally substituted radical from theseries comprising alkyl, alkenyl, alkinyl and aralkyl,

and wherein furthermore

the radicals R¹, R² and R⁴ have the meanings given above,

if the guanidine derivatives of the formula (I) which are obtainable bythe preparation process described above under (a) and in which R¹represents hydrogen, R³ represents hydrogen or an optionally substitutedradical from the series comprising alkyl, cycloalkyl, alkenyl, alkinyland aralkyl, M represents hydrogen or an optionally substituted radicalfrom the series comprising alkyl, alkenyl, alkinyl and aralkyl, and theradicals R² and R⁴ have the meanings given above, are reacted withhalogen/sulphur compounds of the formula (IV)

    R.sup.5 --S(O).sub.m --X.sup.1                             (IV)

in which

X¹ represents fluorine, chlorine or bromine and

m and R⁵ has the meanings given above,

and/or with halogen/sulphur compounds of the formula (V)

    R.sup.6 --S(O).sub.n --X.sup.2                             (V)

in which

X² represents fluorine, chlorine or bromine and

n and R⁶ have the meanings given above, if appropriate in the presenceof acid acceptors and, if appropriate, in the presence of diluents; or

(c) in the case in which R³ represents hydrogen or an optionallysubstituted radical from the series comprising alkyl, cycloalkyl,alkenyl, alkinyl and aralkyl, and M and the radicals R¹, R² and R⁴ havethe meanings given above, if isothioureas of the formula (VI) ##STR11##in which R¹⁵ represents optionally substituted alkyl or aralkyl and

M and the radicals R¹ and R² have the meanings given above,

are reacted with amino compounds of the formula (III) ##STR12## in whichR³ represents hydrogen or an optionally substituted radical from theseries comprising alkyl, cycloalkyl, alkenyl, alkinyl and aralkyl and R⁴has the meaning given above,

or with hydrochlorides of amino compounds of the formula (III), ifappropriate in the presence of acid acceptors and, if appropriate, inthe presence of diluents, and, if required, the reaction products aretreated with acids; or

(d) in the case in which R³ represents hydrogen or an optionallysubstituted radical from the series comprising alkyl, cycloalkyl,alkenyl, alkinyl and aralkyl, and M and the radicals R¹, R² and R⁴ havethe meanings given above, if guanidine derivatives of the formula (I) inwhich

R³ represents the radical --S(O)_(n) --R⁶, wherein

n and R⁶ have the meanings given above, and

M and the radicals R¹, R² and R⁴ have the meanings given above,

are reacted with amino compounds of the formula (III) ##STR13## in whichR³ represents hydrogen or an optionally substituted radical from theseries comprising alkyl, cycloalkyl, alkenyl, alkinyl and aralkyl, and

R⁴ has the meaning given above,

or with hydrochlorides of amino compounds of the formula (III), ifappropriate in the presence of acid acceptors and, if appropriate, inthe presence of diluents; or (e) in the case in which M represents oneequivalent of a metal or represents an ammonium radical which isoptionally substituted by alkyl, alkenyl, alkinyl and/or aralkyl, andthe radicals R¹, R², R³ and R⁴ have the meanings given above, ifguanidine derivatives of the formula (I) in which

M represents hydrogen, and

the radicals R¹, R², R³ and R⁴ have the meanings given above, arereacted with metal hydroxides, hydrides or alkanolates or withorganometallic compounds or with ammonia or appropriate amines, ifappropriate in the presence of diluents; or

(f) in the case in which 1:1 adducts of guanidine derivatives of theformula (I) with strong acids are to be prepared, if guanidinederivatives of the formula (I) in which

M and the radicals R¹, R², R³ and R⁴ have the meanings given above, arereacted with strong acids, if appropriate using inert diluents.

The new guanidine derivatives of the formula (I) and their 1:1 adductswith strong acids are distinguished by powerful herbicidal activityand/or are suitable for regulating the growth of certain plants.

Surprisingly, the new compounds of the formula (I) have a substantiallybetter herbicidal and plant growth-regulating action than previouslyknown guanidines having the same direction of action, and exhibit goodselectivity in cotton and in various species of cereal.

The invention preferably relates to compounds of the formula (I) inwhich

R¹ represents hydrogen or the radical --S(O)_(m) --R⁵,

wherein

m represents the numbers zero, 1 or 2 and

R⁵ represents alkyl having up to 6 carbon atoms which is optionallysubstituted by halogen [such as, in particular, fluorine, chlorineand/or bromine],

and wherein furthermore

R⁵ represents the radical ##STR14## wherein R¹⁶ and R¹⁷ are identical ordifferent and represent hydrogen, halogen [such as, in particular,fluorine, chlorine and/or bromine], cyano, nitro, C₁ -C₆ -alkyl [whichis optionally substituted by fluorine, chlorine, bromine, cyano,carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylaminocarbonyl, di-(C₁-C₄ -alkyl)-aminocarbonyl, hydroxyl, C₁ -C₄ -alkoxy, formyloxy, C₁ -C₄-alkyl-carbonyloxy, C₁ -C₄ -alkoxy-carbonyloxy, C₁ -C₄-alkylamino-carbonyloxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl, C₁-C₄ -alkylsulphonyl, di-(C₁ -C₄ -alkyl)-aminosulphonyl, C₃ -C₆-cycloalkyl or phenyl], C₂ -C₆ -alkenyl [which is optionally substitutedby fluorine, chlorine, bromine, cyano, C₁ -C₄ -alkoxy-carbonyl, carboxylor phenyl], C₁ -C₄ -alkoxy [which is optionally substituted by fluorine,chlorine, bromine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄-alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl], C₃ -C₆-alkenoxy [which is optionally substituted by fluorine, chlorine,bromine, cyano or C₁ -C₄ -alkoxy-carbonyl], C₃ -C₆ -alkinoxy or theradical --S(O)_(p) --R¹⁸, wherein p represents the numbers zero, 1 or 2and R¹⁸ represents C₁ -C₄ -alkyl [which is optionally substituted byfluorine, chlorine, bromine, cyano or C₁ -C₄ -alkoxycarbonyl], C₃ -C₆-alkenyl, C₃ -C₆ -alkinyl, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylamino or di(C₁-C₄ -alkyl)-amino, or represents phenyl or phenoxy, C₁ -C₄-alkyl-carbonylamino, C₁ -C₄ -alkoxy-carbonylamino, C₁ -C₄-alkylamino-carbonylamino, di-(C₁ -C₄ -alkyl)-amino-carbonylamino or theradical --CO--R¹⁹, wherein R¹⁹ represents C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy,C₃ -C₆ -alkenoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylamino or di(C₁ -C₄-alkyl)-amino [which is optionally substituted by fluorine and/orchlorine], or represents C₁ -C₄ -alkylsulphonyloxy, di-(C₁ -C₄-alkyl)-aminosulphonylamino or the radical --CH═N--R²⁰, wherein R²⁰represents C₁ -C₆ -alkyl which is optionally substituted by fluorine,chlorine, cyano, carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylthio, C₁-C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl, benzyl which isoptionally substituted by fluorine or chlorine, C₃ -C₆ -alkenyl or C₃-C₆ -alkinyl which is optionally substituted by fluorine or chlorine,phenyl which is optionally substituted by fluorine, chlorine, bromine,C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, trifluoromethyl, trifluoromethoxy ortrifluoromethylthio, C₃ -C₆ -alkenoxy, C₃ -C₆ -alkinoxy, benzyloxy or C₁-C₆ -alkoxy which is optionally substituted by fluorine and/or chlorine,or represents amino, C₁ -C₄ -alkylamino, di-(C₁ -C₄ -alkyl)-amino,phenylamino, C₁ -C₄ -alkyl-carbonylamino, C₁ -C₄ -alkoxycarbonylamino orC₁ -C₄ -alkyl-sulphonylamino, or represents phenylsulphonylamino whichis optionally substituted by fluorine, chlorine, bromine or methyl;

and wherein furthermore

R⁵ represents the radical ##STR15## wherein R²¹ represents hydrogen orC₁ -C₃ -alkyl and

R²² and R²³ are identical or different and represent hydrogen, fluorine,chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl [which is optionallysubstituted by fluorine and/or chlorine], C₁ -C₄ -alkoxy [which isoptionally substituted by fluorine and/or chlorine], carboxyl, C₁ -C₄-alkoxycarbonyl, C₁ -C₄ -alkylsulphonyl or di-(C₁ -C₄-alkyl)-aminosulphonyl;

and wherein furthermore

R⁵ represents the radical ##STR16## wherein R²⁴ and R²⁵ are identical ordifferent and represent hydrogen, fluorine, chlorine, bromine, nitro,cyano, C₁ -C₄ -alkyl [which is optionally substituted by fluorine and/orchlorine] or C₁ -C₄ -alkoxy [which is optionally substituted by fluorineand/or chlorine];

and wherein furthermore ##STR17## R⁵ represents the radical wherein

R²⁶ and R²⁷ are identical or different and represent hydrogen, fluorine,chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl [which is optionallysubstituted by fluorine and/or chlorine], C₁ -C₄ -alkoxy [which isoptionally substituted by fluorine and/or chlorine], C₁ -C₄ -alkylthio,C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl [which are optionallysubstituted by fluorine and/or chlorine], and di-(C₁ -C₄-alkyl)-aminosulphonyl or C₁ -C₄ -alkoxy-carbonyl, and whereinfurthermore

R⁵ represents the radical ##STR18## wherein R²⁸ and R²⁹ are identical ordifferent and represent hydrogen, fluorine, chlorine, bromine, C₁ -C₄-alkyl [which is optionally substituted by fluorine and/or bromine], C₁-C₄ -alkoxy [which is optionally substituted by fluorine and/orchlorine], C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄-alkylsulphonyl [which are optionally substituted by fluorine and/orchlorine] or di-(C₁ -C₄ -alkyl)-aminosulphonyl,

and wherein furthermore

R⁵ represents the radical ##STR19## wherein R³⁰ and R³¹ are identical ordifferent and represent hydrogen, fluorine, chlorine, bromine, cyano,nitro, C₁ -C₄ -alkyl [which is optionally substituted by fluorine and/orchlorine], C₁ -C₄ -alkoxy [which is optionally substituted by fluorineand/or chlorine], C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄-alkylsulphonyl [which is optionally substituted by fluorine and/orchlorine], di-(C₁ -C₄ -alkyl)-aminosulphonyl or C₁ -C₄ -alkoxy-carbonyl,and

Z represents oxygen, sulphur or the grouping N--Z¹,

wherein

Z¹ represents hydrogen, C₁ -C₄ -alkyl [which is optionally substitutedby fluorine, chlorine, bromine or cyano], C₃ -C₆ -cycloalkyl, benzyl,phenyl [which is optionally substituted by fluorine, chlorine, bromineor nitro], C₁ -C₄ -alkyl-carbonyl, C₁ -C₄ -alkoxy-carbonyl or di-(C₁ -C₄-alkyl)-aminocarbonyl,

and in which furthermore

R² represents the radical ##STR20## wherein R³² and R³⁴ are identical ordifferent and represent hydrogen, fluorine, chlorine, bromine, C₁ -C₄-alkyl [which is optionally substituted by fluorine and/or chlorine] orC₁ -C₄ -alkoxy [which is optionally substituted by fluorine and/orchlorine], with the proviso that at least one of the radicals R³² andR³⁴ is not hydrogen, and

R³³ represents hydrogen, fluorine, chlorine, bromine, cyano or C₁ -C₄-alkyl [which is optionally substituted by fluorine and/or chlorine];

and in which furthermore

R² represents the radical ##STR21## wherein R³⁵ and R³⁶ are identical ordifferent and represent hydrogen, fluorine, chlorine, bromine, C₁ -C₄-alkyl [which is optionally substituted by fluorine and/or chlorine], C₁-C₄ -alkoxy [which is optionally substituted by fluorine and/orchlorine], C₁ -C₄ -alkylamino or di-(C₁ -C₄ -alkyl)-amino, with theproviso that at least one of the radicals R³⁵ and R³⁶ is not hydrogen;

and in which furthermore

R² represents the radical ##STR22## wherein R³⁷ represents hydrogen,fluorine, chlorine, bromine, C₁ -C₄ -alkyl [which is optionallysubstituted by fluorine and/or chlorine] or C₁ -C₄ -alkoxy [which isoptionally substituted by fluorine and/or chlorine],

R³⁸ represents hydrogen, fluorine, chlorine, bromine, C₁ -C₄ -alkyl[which is optionally substituted by fluorine and/or chlorine], cyano,formyl, C₁ -C₄ -alkyl-carbonyl or C₁ -C₄ -alkoxycarbonyl, and

R³⁹ represents C₁ -C₄ -alkyl [which is optionally substituted byfluorine and/or chlorine], C₁ -C₄ -alkoxy [which is optionallysubstituted by fluorine and/or chlorine], amino, C₁ -C₄ -alkylamino ordi-(C₁ -C₄ -alkyl)-amino, or

R³⁸ and R³⁹ together represent C₃ -C₄ -alkanediyl,

and in which furthermore

R² represents the radical ##STR23## wherein R⁴⁰ and R⁴¹ are identical ordifferent and represent C₁ -C₄ -alkyl [which is optionally substitutedby fluorine and/or chlorine] or C₁ -C₄ -alkoxy [which is optionallysubstituted by fluorine and/or chlorine];

and in which furthermore

R³ represents hydrogen, C₁ -C₄ -alkyl [which is optionally substitutedby fluorine, chlorine, bromine, cyano, hydroxyl or C₁ -C₂ -alkoxy], C₃-C₆ -cycloalkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, benzyl [which isoptionally substituted by fluorine, chlorine or methyl] or the radical--S(O)_(n) --R⁶,

wherein

n represents the numbers zero, 1 or 2 and

R⁶ has the preferred meaning given above for R⁵, but is not identical toR⁵ in each individual case;

and in which furthermore

R⁴ represents hydrogen or hydroxyl, with the proviso that then at leastone of the radicals R¹ and R³ is not hydrogen;

and in which furthermore

--in the case in which R³ is not hydrogen--R⁴ represents C₁ -C₆ -alkyl[which is optionally substituted by fluorine, chlorine, bromine, cyano,carboxyl, C₁ -C₄ -alkoxy-carbonyl, hydroxyl or C₁ -C₄ -alkoxy], C₃ -C₆-cycloalkyl [which is optionally interrupted by a --SO₂ -- bridge], C₃-C₆ -alkenyl, C₃ -C₆ -alkinyl, benzyl or phenylethyl [which isoptionally substituted by fluorine, chlorine and/or methyl] or phenyl[which is optionally substituted by fluorine, chlorine, bromine,hydroxyl, cyano, nitro, amino, C₁ -C₄ -alkyl, trifluoromethyl, C₁ -C₄-alkoxy, trifluoromethoxy, C₁ -C₄ -alkylthio, trifluoromethylthio,aminosulphonyl or C₁ -C₄ -alkoxycarbonyl], or

R³ and R⁴ together represent C₄ -C₆ -alkanediyl which is optionallyinterrupted by an oxygen bridge or by a bridge ##STR24## wherein R⁷represents C₁ -C₄ -alkyl, C₁ -C₄ -alkylcarbonyl or phenyl [which isoptionally substituted by fluorine, chlorine, bromine, cyano, nitro, C₁-C₄ -alkyl, trifluoromethyl or C₁ -C₄ -alkoxy];

and in which furthermore

R⁴ represents the radical --X--R⁸,

wherein

X represents oxygen, sulphur, --SO-- or --SO₂ -- and

R⁸ represents C₁ -C₆ -alkyl [which is optionally substituted byfluorine, chlorine, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio, C₁ -C₄-alkylsulphinyl or C₁ -C₄ -alkylsulphonyl], C₃ -C₆ -alkenyl, C₃ -C₆-alkinyl, C₃ -C₆ -cycloalkyl, benzyl [which is optionally substituted byfluorine, chlorine or methyl] or phenyl [which is optionally substitutedby fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl,trifluoromethyl, C₁ -C₄ -alkoxy, trifluoromethoxy, C₁ -C₄ -alkylthio ortrifluoromethylthio];

and in which furthermore

R⁴ represents the radical ##STR25## wherein R⁹ represents hydrogen or C₁-C₄ -alkyl and

R¹⁰ represents C₁ -C₄ -alkyl [which is optionally substituted byfluorine, chlorine, bromine, cyano, C₁ -C₄ -alkoxy or C₁ -C₄-alkoxy-carbonyl], C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, C₃ -C₆ -cycloalkyl[which is optionally interrupted by a --SO₂ bridge], benzyl orphenylethyl [which are optionally substituted by fluorine, chlorine ormethyl], phenyl [which is optionally substituted by fluorine, chlorine,bromine, nitro, cyano, C₁ -C₄ -alkyl, trifluoromethyl, C₁ -C₄ -alkoxy,trifluoromethoxy, C₁ -C₄ -alkylthio or trifluoromethylthio], pyrimidyl,C₁ -C₄ -alkyl-carbonyl, benzoyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄-alkylsulphonyl or phenylsulphonyl [which is optionally substituted byfluorine, chlorine, bromine or methyl] or

R⁹ and R¹⁰ together represent C₄ -C₆ -alkanediyl [which is optionallyinterrupted by an oxygen bridge];

and in which furthermore

R⁴ represents the radical ##STR26## wherein R¹¹ represents hydrogen orC₁ -C₄ -alkyl and

R¹² represents C₁ -C₄ -alkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, C₃ -C₆-cycloalkyl, benzyl or phenylethyl [which are optionally substituted byfluorine, chlorine or methyl] or phenyl [which is optionally substitutedby fluorine, chlorine, bromine, C₁ -C₄ -alkyl, trifluoromethyl, cyano,nitro, C₁ -C₄ -alkoxy or trifluoromethoxy], or

R¹¹ and R¹² together represent C₄ -C₆ -alkanediyl;

and in which furthermore

R⁴ represents tri-(C₁ -C₄ -alkyl)-silyl or the radical ##STR27## whereinq represents the numbers zero or 1,

Y represents oxygen or sulphur and

R¹³ and R¹⁴ are identical or different and individually represent C₁ -C₄-alkyl [which is optionally substituted by fluorine, chlorine, cyano ormethoxy], C₂ -C₄ -alkenyl, C₃ -C₄ -alkinyl, benzyl [which is optionallysubstituted by fluorine, chlorine or methyl], phenyl [which isoptionally substituted by fluorine, chlorine or methyl], C₁ -C₄ -alkoxy[which is optionally substituted by fluorine, chlorine, cyano ormethoxy], C₂ -C₄ -alkenoxy, C₃ -C₄ -alkinoxy, benzyloxy [which isoptionally substituted by fluorine, chlorine and/or methyl], phenoxy[which is optionally substituted by fluorine, chlorine, bromine, cyano,nitro, methyl, trifluoromethyl or methoxy], C₁ -C₄ -alkylthio [which isoptionally substituted by fluorine, chlorine, cyano or methoxy], C₂ -C₄-alkenylthio, benzylthio [which is optionally substituted by fluorine,chlorine or methyl], C₃ -C₄ -alkinylthio, phenylthio [which isoptionally substituted by fluorine, chlorine, bromine, cyano, nitro,methyl, trifluoromethyl or methoxy], amino, C₁ -C₄ -alkylamino or di-(C₁-C₄ -alkyl)-amino, or together represent C₂ -C₅ -alkanedioxy, oxy-C₁ -C₃-alkylamino or C₁ -C₃ -alkanediamino;

and in which furthermore

R⁴ represents a five-membered or six-membered heterocyclic structurewhich contains 1 to 3 nitrogen atoms and/or an oxygen or sulphur atomand is optionally substituted by fluorine, chlorine, bromine, C₁ -C₄-alkyl, trifluoromethyl, nitro, cyano or C₁ -C₄ -alkoxy;

and in which furthermore

M represents hydrogen, one equivalent of sodium, potassium, magnesium,calcium, aluminium, manganese, iron, cobalt or nickel, an ammoniumradical which is optionally substituted by C₁ -C₆ -alkyl [which isoptionally substituted by chlorine], C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyland/or benzyl [which is optionally substituted by fluorine, chlorine ormethyl], or --in the case in which M is bonded to the same nitrogen atomas R² --also represents C₁ -C₆ -alkyl [which is optionally substitutedby fluorine, chlorine or cyano], C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl orbenzyl.

The invention furthermore preferably relates to 1:1 adducts of compoundsof the formula (I)--as defined above--with hydrohalic acids, such ashydrogen fluoride, chloride, bromide and iodide, with sulphuric acid,phosphoric acid, with alkanesulphonic acids which have up to 4 carbonatoms and are optionally substituted by fluorine or chlorine, orbenzene- or naphthalene-sulphonic acids which are optionally substitutedby fluorine, chlorine or methyl.

The invention relates in particular to compounds of the formula (I)

(A)

R¹ represents the radical --S(O)_(m) --R⁵,

wherein

m represents the number 2 and

R⁵ represents the radical ##STR28## wherein R¹⁶ represents fluorine,chlorine, bromine, methyl, trifluoromethyl, C₁ -C₂ -alkoxy,difluoromethoxy, trifluoromethoxy, phenyl or C₁ -C₂ -alkoxycarbonyl and

R¹⁷ represents hydrogen;

and in which furthermore

R² represents the radical ##STR29## wherein R³⁷ represents hydrogen,methyl or methoxy,

R³⁸ represents hydrogen, chlorine, methyl, acetyl or methoxycarbonyl and

R³⁹ represents C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy or, together with R³⁸,represents C₃ -C₄ -alkanediyl;

and in which furthermore

R³ represents hydrogen, methyl or the radical --S(O)_(n) --R⁶,

wherein

n represents the number 2 and

R⁶ has the particularly preferred meaning given above for R⁵ ;

and in which furthermore

R⁴ represents hydroxyl, C₁ -C₄ -alkoxy, C₃ -C₄ -alkenoxy, C₃ -C₄-alkinoxy, benzyloxy or the radical ##STR30## wherein R⁹ representshydrogen or methyl and

R¹⁰ represents C₁ -C₃ -alkyl, phenyl, acetyl, methoxycarbonyl,phenylsulphonyl or p-toluenesulphonyl;

and in which furthermore

M represents hydrogen, sodium, potassium or one equivalent of magnesiumor calcium; and--in the case in which M represents hydrogen--the 1:1adducts of the compounds defined above with hydrochloric acid, sulphuricacid, benzenesulphonic acid and p-toluenesulphonic acid;

or in which

(B)

R¹ represents hydrogen or the radical --S(O)_(m) --R⁵,

wherein

m represents the numbers zero, 1 or 2 and

R⁵ represents the radical ##STR31## wherein R¹⁶ and R¹⁷ representhydrogen or

R¹⁶ represents chlorine, nitro, methyl, trifluoromethyl or methoxy and

R¹⁷ represents fluorine, chlorine, bromine, methyl, trifluoromethyl,cyano, nitro or methoxy;

and in which furthermore

R² represents the radical ##STR32## wherein R³⁷ represents hydrogen,methyl or methoxy,

R³⁸ represents hydrogen, chlorine, methyl, acetyl or methoxycarbonyl and

R³⁹ represents C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy or

R³⁸ and R³⁹ together represent C₃ -C₄ -alkanediyl,

and in which furthermore

R³ represents hydrogen, methyl or the radical --S(O)_(n) --R⁶,

wherein

n represents the numbers zero, 1 or 2 and

R⁶ has the particularly preferred meaning given above for R⁵ ;

and in which furthermore

R⁴ represents hydroxyl, with the proviso that then at least one of theradicals R¹ and R³ is not hydrogen;

and in which furthermore

R⁴ represents C₁ -C₄ -alkoxy, C₃ -C₄ -alkenoxy, C₃ -C₄ -alkinoxy,benzoyloxy or the radical ##STR33## wherein R⁹ represents hydrogen ormethyl and

R¹⁰ represents C₁ -C₃ -alkyl, phenyl, acetyl, methoxycarbonyl,phenylsulphonyl or p-toluenesulphonyl;

and in which furthermore

M represents hydrogen, sodium, potassium or one equivalent of magnesiumor calcium, and--in the case in which M represents hydrogen--the 1:1adducts of the compounds defined above with hydrochloric acid, sulphuricacid, benzenesulphonic acid and p-toluenesulphonic acid;

or in which

C

R¹ represents hydrogen or the radical --S(O)_(m) --R⁵,

wherein

m represents the numbers zero, 1 or 2 and

R⁵ represents the radical ##STR34## wherein R¹⁶ represents hydrogen,fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, C₁ -C₂-alkoxy, difluoromethoxy, trifluoromethoxy, phenyl or C₁ -C₂-alkoxy-carbonyl and

R¹⁷ represents hydrogen, fluorine, chlorine, bromine, nitro, methyl,trifluoromethyl, C₁ -C₂ -alkoxy, difluoromethoxy or trifluoromethoxy,

and in which furthermore

R² represents the radical ##STR35## wherein R³⁷ represents hydrogen,methyl or methoxy,

R³⁸ represents hydrogen, chlorine, methyl, acetyl or methoxycarbonyl and

R³⁹ represents C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy or

R³⁸ and R³⁹ together represent C₃ -C₄ -alkanediyl,

and in which furthermore

R³ represents hydrogen, with the proviso that then R¹ is not hydrogen,or represents optionally hydroxyl-substituted C₁ -C₄ -alkyl, or C₅ -C₆-cycloalkyl, C₃ -C₄ -alkenyl or C₃ -C₄ -alkinyl; benzyl or the radical--S(O)_(n) --R⁶,

wherein

n represents the numbers zero, 1 or 2 and

R⁶ has the particularly preferred meaning given above for R⁵ ;

and in which furthermore

R⁴ represents C₁ -C₄ -alkyl which is optionally substituted by chlorine,cyano, C₁ -C₃ -alkoxy-carbonyl, hydroxyl or C₁ -C₂ -alkoxy, orrepresents C₃ -C₆ -cycloalkyl, C₃ -C₄ -alkenyl, C₃ -C₄ -alkinyl orbenzyl, or represents phenyl which is optionally substituted byfluorine, chlorine, bromine, nitro, cyano, aminosulphonyl, hydroxyl,amino, methyl, trifluoromethyl, methoxy, trifluoromethoxy, methylthio,trifluoromethylthio or C₁ -C₂ -alkoxy-carbonyl, or--in the case in whichR¹ is not hydrogen--also represents hydrogen;

and in which furthermore

M represents hydrogen, sodium, or potassium or one equivalent ofmagnesium or calcium, or C₁ -C₄ -alkyl-, di-(C₁ -C₄ -alkyl)- or tri-(C₁-C₄ -alkyl)-ammonium; and--in the case in which M representshydrogen--the 1:1 adducts of the compounds defined above withhydrochloric acid, sulphuric acid, benzenesulphonic acid andp-toluenesulphonic acid;

or in which

(D)

R¹ represents the radical --S(O)_(m) --R⁵,

wherein

m represents the number 2 and

R⁵ represents the radical ##STR36## wherein R¹⁶ represents fluorine,chlorine, bromine, methyl, trifluoromethyl, C₁ -C₂ -alkoxy,difluoromethoxy, trifluoromethoxy or C₁ -C₂ -alkoxy-carbonyl and

R¹⁷ represents hydrogen;

and in which furthermore

R² represents the radical ##STR37## wherein R⁴⁰ represents methyl,methoxy or ethoxy and

R⁴¹ represents methyl, methoxy or ethoxy;

and in which furthermore

R³ represents hydrogen, methyl or the radical --S(O)_(n) --R⁶,

wherein

n represents the number 2 and

R⁶ has the particularly preferred meaning given above for R⁵ ;

and in which furthermore

R⁴ represents hydroxyl, C₁ -C₄ -alkoxy, C₃ -C₄ -alkenoxy, C₃ -C₄-alkinoxy, benzyloxy or the radical ##STR38## wherein R⁹ representshydrogen or methyl and

R¹⁰ represents C₁ -C₃ -alkyl, phenyl, acetyl, methoxycarbonyl,phenylsulphonyl or p-toluenesulphonyl;

and in which furthermore

M represents hydrogen, sodium or potassium or one equivalent ofmagnesium or calcium; and--in the case in which M representshydrogen--the 1:1 adducts of the compounds defined above withhydrochloric acid, sulphuric acid, benzenesulphonic acid andp-toluenesulphonic acid;

or in which

(E)

R¹ represents hydrogen or the radical --S(O)_(m) --R⁵,

wherein

m represents the numbers zero, 1 or 2 and

R⁵ represents the radical ##STR39## wherein R¹⁶ and R¹⁷ both representhydrogen, or

R¹⁶ represents chlorine, nitro, methyl, trifluoromethyl or methoxy and

R¹⁷ represents fluorine, chlorine, bromine, methyl, trifluoromethyl,cyano, nitro or methoxy;

and in which furthermore

R² represents the radical ##STR40## wherein R⁴⁰ represents methyl,methoxy or ethoxy and

R⁴¹ represents methyl, methoxy or ethoxy;

and in which furthermore

R³ represents hydrogen, methyl or the radical --S(O)_(n) --R⁶,

wherein

n represents the numbers zero, 1 or 2 and

R⁶ has the particularly preferred meaning given above for R⁵ ;

and in which furthermore

R⁴ represents hydroxyl, with the proviso that then at least one of theradicals R¹ and R³ is not hydrogen;

and in which furthermore

R⁴ represents C₁ -C₄ -alkoxy, C₃ -C₄ -alkenoxy, C₃ -C₄ -alkinoxy,benzyloxy or the radical ##STR41## wherein R⁹ represents hydrogen ormethyl and

R¹⁰ represents C₁ -C₃ -alkyl, phenyl, acetyl, methoxycarbonyl,phenylsulphonyl or p-toluenesulphonyl;

and in which furthermore

M represents hydrogen, sodium or potassium or one equivalent ofmagnesium or calcium, and--in the case in which M representshydrogen--the 1:1 adducts of the compounds defined above withhydrochloric acid, sulphuric acid, benzenesulphonic acid andp-toluenesulphonic acid;

or in which

(F)

R¹ represents hydrogen or the radical --S(O)_(m) --R⁵,

wherein

m represents the numbers zero, 1 or 2 and

R⁵ represents the radical ##STR42## wherein R¹⁶ represents hydrogen,fluorine, chlorine, bromine, nitro, methyl, trifluoromethyl, C₁ -C₂-alkoxy, difluoromethoxy, trifluoromethoxy or C₁ -C₂ -alkoxy and

R¹⁷ represents hydrogen, fluorine, chlorine, bromine, nitro, methyl,trifluoromethyl, C₁ -C₂ -alkoxy, difluoromethoxy or trifluoromethoxy,

and in which furthermore

R² represents the radical ##STR43## wherein R⁴⁰ represents methyl,methoxy or ethoxy and

R⁴¹ represents methyl, methoxy or ethoxy;

and in which furthermore

R³ represents hydrogen, optionally hydroxyl-substituted C₁ -C₄ -alkyl,C₅ -C₆ -cycloalkyl, C₃ -C₄ -alkenyl, C₃ -C₄ -alkinyl, benzyl or theradical --S(O)_(n) --R⁶,

wherein

n represents the numbers zero, 1 or 2 and

R⁶ has the particularly preferred meaning given above for R⁵ ;

and in which furthermore

R⁴ represents C₁ -C₄ -alkyl which is optionally substituted by chlorine,cyano, C₁ -C₃ -alkoxycarbonyl, hydroxyl or C₁ -C₂ -alkoxy, or representsC₅ -C₆ -cycloalkyl, C₃ -C₄ -alkenyl, C₃ -C₄ -alkinyl or benzyl, orrepresents phenyl which is optionally substituted by fluorine, chlorine,bromine, nitro, cyano, aminosulphonyl, hydroxyl, amino, methyl,trifluoromethyl, methoxy, trifluoromethoxy, methylthio,trifluoromethylthio or C₁ -C₂ -alkoxy-carbonyl, or--in the case in whichat least one of the radicals R₁ and R³ is not hydrogen--also representshydrogen;

and in which furthermore

M represents hydrogen, sodium or potassium or one equivalent ofmagnesium or calcium, or C₁ -C₄ -alkyl-, di-(C₁ -C₄ -alkyl)- or tri-(C₁-C₄ -alkyl)-ammonium; and--in the case in which M representshydrogen--the 1:1 adducts of the compounds defined above withhydrochloric acid, sulphuric acid, benzenesulphonic acid andp-toluenesulphonic acid.

If, for example O-isopropyl-hydroxylamine hydrochloride and2-cyanoamino-4-methoxy-6-methyl-pyrimidine are used as startingmaterials for process variant (a), the course of the reaction can berepresented by the following equation: ##STR44##

If, for example, 2-difluoromethoxy-benzenesulphonyl chloride andN'-(4-methoxy-6-methyl-s-triazin-2-yl)-N"-dimethylamino-guanidine areused as starting materials for process variant (b), the course of thereaction can be represented by the following equation: ##STR45##

If, for example,N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-N"-(2-fluorobenzenesulphonyl)-S-methyl-isothioureaand diethylamine are used as starting materials for process variant (c),and the ammonium salt initially obtained is treated with hydrochloricacid, the course of the reaction can be represented by the followingequation: ##STR46##

If, for example,N'-(4,6-dimethoxy-s-triazin-2-yl)-N"-methoxy-N",N"'-bis-(2-trifluoromethyl-benzenesulphonyl)-guanidineand ammonia are used as starting materials for process variant (d), thecourse of the reaction can be represented by the following equation:##STR47##

If, for example,N'-(4,6-dimethoxy-pyrimidin-2-yl)-N"-methoxy-N"'-(2-trifluoro-methoxy-benzenesulphonyl)-guanidineand potassium ethanolate are used as starting materials for processvariant (e), the course of the reaction can be represented by thefollowing equation: ##STR48##

If, for example,N'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methyl-N"'-(2-methoxycarbonyl-benzenesulphonyl)-guanidineand trifluoromethane-sulphonic acid are used as starting materials forprocess variant (f), the course of the reaction can be represented bythe following equation: ##STR49##

If, for example,N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-N"-(2-methyl-benzenesulphonyl)-S-methyl-isothioureaand N,N-dimethylhydrazine are used as starting substances for processvariant (e), the course of the reaction can be outlined by the followingequation: ##STR50##

Formula (II) gives a general definition of the cyano compounds to beused as starting materials for process variant (a). In this formula, M¹preferably represents hydrogen, C₁ -C₆ -alkyl [which is optionallysubstituted by fluorine, chlorine or cyano], C₃ -C₆ -alkenyl, C₃ -C₆-alkinyl or benzyl, in particular hydrogen, and R² preferably orparticularly has the same meaning as given above within the framework ofthe definition of substituents for formula (I) as being preferred orparticularly preferred respectively.

The following may be mentioned as examples of starting materials of theformula (II):

2-cyanoamino-4,6-dimethyl-pyrimidine,2-cyanoamine-4-methoxy-6-methyl-pyrimidine,2-cyanoamino-4,6-dimethoxy-pyrimidine,2-cyanoamino-4-ethoxy-6-methyl-pyrimidine,2-cyanoamino-4-methyl-6-propoxy-pyrimidine,2-cyanoamino-4-methyl-6-isopropoxy-pyrimidine,2-cyanoamino-4-methyl-6-butoxy-pyrimidine,2-cyanoamino-4-methyl-6-isobutoxy-pyrimidine,2-(cyano-N-methyl-amino)-4,6-dimethyl-pyridimine,2-(cyano-N-methyl-amino)-4-methoxy-6-methyl-pyrimidine,2-cyanoamino-4,6-dimethyl-s-triazine,2-cyanoamino-4-methoxy-6-methyl-s-triazine,2-cyanoamino-4,6-dimethoxy-s-triazine,2-cyanoamino-4-ethoxy-6-methyl-s-triazine,2-cyanoamino-5-chloro-4,6-dimethyl-pyrimidine and2-cyanoamino-4,5,6-trimethyl-pyrimidine.

The compound 2-cyanoamino-4,6-dimethyl-pyrimidine of formula (II) isknown (see J. Chem. Soc. 1953, 1725-1730, 1725). The compounds of theformula (II) are essentially obtained by the following two synthesisroutes:

(a¹)

in general by reaction of alkali metal or alkaline earth metal salts ofcyanamide--such as, for example, sodium cyanamide or calciumcyanamide--with halogen compounds of the formula (VII)

    Hal.sup.1 --R.sup.2                                        (VII)

in which

R² has the meaning given above and

Hal¹ represents fluorine, chlorine, bromine or iodine, in particularchlorine,

if appropriate in the presence of inert diluents, such as, for example,acetone, acetonitrile or dimethylformamide, at temperatures between 0°C. and 150° C., preferably between 10° C. and 100° C.; after thevolatile component has been distilled off and the residue has beendissolved in water, the cyano compounds of the formula (II) can beprecipitated by acidification, for example with hydrochloric acid, andcan be isolated by filtration under suction; or

(a²)

in the case in which R² represents a substituted pyrimidinyl radical, byreaction of cyanoguanidine ("dicyanodiamide") with β-dicarbonylcompounds, such as, for example, acetylacetone, (see J. Chem. Soc. 1953,1725-1730), acetoacetic acid esters (see J. Prakt. Chem. 77, (1908), 542and J. Chem. Soc. 1948, 586) or malonic acid esters (see German Pat.specification No. 158,591).

The 2-cyanoamino-4-hydroxy-6-methyl- or -4,6-dihydro-pyrimidinesobtained from acetoacetic acid esters or malonic acid esters can beconverted to the corresponding 2-cyanoamino-4-alkoxy-6-methyl- or-4,6-dialkoxy-pyrimidines in a customary manner by reaction withalkylating agents, such as, for example, dimethyl sulphate or diethylsulphate, if appropriate in the presence of diluents, such as, forexample, water, methanol, ethanol, n- and iso-propanol, acetone, dioxaneor dimethylformamide, and in the presence of acid-binding agents, suchas, for example, sodium hydroxide, potassium hydroxide, sodium carbonateor potassium carbonate. If necessary, in order to avoid N-alkylation,acylation is carried out with an acylating agent, such as, for example,acetic anhydride or acetyl chloride, and deacylation is effected withaqueous acids or bases after the alkylation.

The halogen compounds of the formula (VII) are known (see J. Chem. Soc.(C) 1966, 2031; Chem. Pharm. Bull. 11 (1963), 1382-1388; and Arch.Pharm. 295 (1962), 649-657).

Amino compounds of the formula (III) which are furthermore to be used asstarting materials for process variant (a) are known and can be preparedby processes which are in themselves known (see Chem. Pharm. Bull. 15(1967), 345-349; Bull. Soc. Chem. France 1958, 664; and Synthesis 1976,682; J. Chem. Soc. 1930, 228 and Helv. Chim. Acta 45 (1962), 1387).

In formula (III), R⁴ preferably has the same meaning as given abovewithin the framework of the definition of substituents for formula (I)as being preferred, and R³ preferably represents hydrogen, C₁ -C₄ -alkyl[which is optionally substituted by fluorine, chlorine, bromine, cyano,hydroxyl or C₁ -C₄ -alkoxy], C₃ -C₆ -cycloalkyl, C₃ -C₆ -alkenyl, C₃ -C₆-alkinyl or benzyl [which is optionally substituted by fluorine,chlorine or methyl].

Particularly preferred starting materials of the formula (III) are thosein which R⁴ has the same meaning as given above within the framework ofthe definition of substituents for formula (I) as being particularlypreferred, and R³ represents hydrogen, optionally hydroxyl-substitutedC₁ -C₄ -alkyl, C₅ -C₆ -cycloalkyl, C₃ -C₄ -alkenyl, C₃ -C₄ -alkinyl orbenzyl.

As starting materials of the formula (III), the following may bementioned as examples: ammonia, methylamine, ethylamine, n- andiso-propylamine, n-, iso-, sec.- and tert.-butylamine, cyclopentylamine,cyclohexylamine, allylamine, propargylamine, benzylamine, aniline,2-fluoro-, 3-fluoro- and 4-fluoro-aniline, 2-chloro-, 3-chloro- and4-chloro-aniline, 2-bromo-, 3-bromo- and 4-bromo-aniline, 2-nitro-,3-nitro- and 4-nitro-aniline, 2-amino-, 3-amino- and4-amino-benzonitrile, 4-amino-benzenesulphonamide, ortho-, meta- andpara-phenylenediamine, ortho-, meta- and para-toluidine,2-trifluoromethyl-, 3-trifluoromethyl- and 4-trifluoromethyl-aniline,2-methoxy-, 3-methoxy- and 4-methoxy-aniline,4-trifluoromethylthio-aniline, 2-amino and 4-amino-benzoic acid methylester, dimethylamine, diethylamine, dipropylamine, diisopropylamine,dibutylamine, dicycloentylamine, dicyclohexylamine, diallylamine,dipropargylamine, dibenzylamine, N-methylaniline,O-methyl-hydroxylamine, O-ethyl-hydroxylamine, O-propylhydroxylamine,O-isopropylhydroxylamine, O-butyl-hydroxylamine,O-isobutyl-hydroxylamine, O-allyl-hydroxylamine,O-propargyl-hydroxylamine, O-benzyl-hydroxylamine,N,O-dimethyl-hydroxylamine, methylhydrazine, N,N-dimethylhydrazine,N,N'-dimethylhydrazine, ethylhydrazine and n- and iso-propylhydrazine aswell as the hydrochlorides of these compounds; phenylhydrazine,acethydrazide, methyl hydrazinoformate, benzenesulphonohydrazide andp-toluenesulphonohydrazide.

Formula (I) and the conditions stated above under (b) give a generaldefinition of the guanidine derivatives to be used a starting materialsin process (b). In this formula--where it relates to the guanidines tobe used as starting materials for process (b):

R¹ preferably represents hydrogen,

R³ preferably represents hydrogen, C₁ -C₄ -alkyl [which is optionallysubstituted by fluorine, chlorine, bromine, cyano, hydroxyl or C₁ -C₄-alkoxy], C₃ -C₆ -cycloalkyl, C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl or benzyl[which is optionally substituted by fluorine, chlorine or methyl],

M represents hydrogen, C₁ -C₆ -alkyl [which is optionally substituted byfluorine, chlorine or cyano], C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl or benzyland

R² and R⁴ preferably have the same meanings as given above within theframework of the definition of substituents for formula (I) as beingpreferred.

Particularly preferred starting materials for process variant (b) arethe guanidine derivatives of the formula (I)

in which

R¹ represents hydrogen,

R³ represents hydrogen, optionally hydroxyl-substituted alkyl, C₅ -C₆-cycloalkyl, C₃ -C₄ -alkenyl, C₃ -C₄ -alkinyl or benzyl,

M represents hydrogen and

R² and R⁴ have the same meanings as given above within the framework ofthe definition of substituents for formula (I) as being particularlypreferred.

The following may be mentioned as examples of guanidine derivatives ofthe formula (I) which are to be employed as starting materials inpreparation process (b): N'-(4,6-dimethyl-pyrimidin-2-yl)-,N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-,N'-(4-ethoxy-6-methyl-pyrimidin-2-yl)-,N'-(4-propoxy-6-methyl-pyrimidin-2-yl)-,N'-(4-isopropoxy-6-methyl-pyrimidin-2-yl)-,N'-(4-butoxy-6-methyl-pyrimidin-2-yl)-,N'-(4-isobutoxy-6-methyl-pyrimidin-2-yl)-,N'-(4,6-dimethoxy-pyrimidin-2-yl)-, N'-(4,6-dimethyl-s-triazin-2-yl)-,N'-(4-methoxy-6-methyl-s-triazin-2-yl)-,N'-(4-ethoxy-6-methyl-s-triazin-2-yl)-,N'-(4,6-dimethoxy-s-triazin-2-yl)-,N'-methyl-N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-,N'-(4,5,6-trimethyl-pyrimidin-2-yl) andN'-(5-chloro-4,6-dimethyl-pyrimidin-2-yl)-guanidine,-N"-methylguanidine, -N"-ethylguanidine, -N"-propyl-guanidine,-N"-isopropyl-guanidine, -N"-butyl-guanidine, -N"-isobutyl-guanidine,-N"-sec.-butyl-guanidine, -N"-tert.-butyl-guanidine,-N"-cyclopentyl-guanidine, -N"-cyclohexyl-guanidine,-N"-allyl-guanidine, -N"-propargyl-guanidine, -N"-benzyl-guanidine,-N"-phenyl-guanidine, -N"-(2-fluoro-phenyl)-, -(3-fluoro-phenyl)- and-(4-fluoro-phenyl)-guanidine, -N"-(2-chloro-phenyl)-,-(3-chloro-phenyl)- and -(4-chloro-phenyl)-guanidine,-N"-(2-bromo-phenyl)-, -(3-bromo-phenyl)- and-(4-bromo-phenyl)-guanidine, -N"-(2-nitro-phenyl)-, -(3-nitro-phenyl)-and -(4-nitro-phenyl)-guanidine, -N"-(2-aminophenyl)-, -(3-aminophenyl)-and -(4-amino-phenyl)-guanidine, -N"-(2-cyano-phenyl)-,-(3-cyano-phenyl)- and -(4-cyano-phenyl)-guanidine,-N"-(4-amino-sulphonyl-phenyl)-guanidine, -N"-(2-hydroxy-phenyl)-,-(3-hydroxy-phenyl)- and -(4-hydroxy-phenyl)-guanidine,-N"-(2-methyl-phenyl)-, -(3-methyl-phenyl)- and-(4-methyl-phenyl)-guanidine, -N"-(2-trifluoromethylphenyl)-,-(3-trifluoromethyl-phenyl)- and -(4-trifluoromethyl-phenyl)-guanidine,-N"-(2-methoxy-phenyl)- -(3-methoxy-phenyl)- and-(4-methoxy-phenyl)-guanidine, -N"-(2-trifluoromethoxy-phenyl)- and-(4-trifluoromethoxyphenyl)-guanidine,-N"-(4-trifluoromethylthio-phenyl)-guanidine,-N"-(2-methoxycarbonylphenyl)- and-(4-methoxycarbonyl-phenyl)-guanidine, -N",N"-dimethyl-guanidine,-N",N"-diethyl-guanidine, -N",N"-dipropyl-guanidine,-N",N"-diisopropyl-guanidine, -N",N"-dibutyl-guanidine,-N",N"-diisobutyl-guanidine. -N",N"-dicyclopentyl-guanidine,-N",N"-dicyclohexyl-guanidine, -N",N"-diallyl-guanidine,-N",N"-dipropargyl-guanidine, -N",N"-dibenzyl-guanidine,-N"-methyl-N"-phenyl-guanidine, -N"-methoxy-guanidine,-N"-ethoxy-guanidine, -N"-propoxy-guanidine, -N"-isopropoxy-guanidine,-N"-butoxy-guanidine, -N"-isobutoxy-guanidine, -N"-allyloxy-guanidine,-N"-propargyloxy-guanidine, -N"-benzyloxy-guanidine,-N"-methyl-N"-methoxy-guanidine, -N"-methylamino-guanidine,-N"-dimethylamino-guanidine, -N"-methyl-N"-methylamino-guanidine,-N"-ethylamino-guanidine, -N"-propylamino-guanidine,-N"-isopropylamino-guanidine, -N"-morpholino-guanidine,-N"-acetamino-guanidine, -N"-methoxycarbonylamino-guanidine,-N"-benzenesulphonylamino-guanidine and-N"-p-toluene-sulphonylamino-guanidine.

The guanidine derivatives of the formula (I) which are to be used asstarting materials for process (b) have largely not yet been describedin the literature and can be prepared by process (a) according to theinvention.

Formulae (IV) and (V) give general definitions of the halogen/sulphurcompounds furthermore to be used as starting materials in process (b).In these formulae, m, n, R⁵ and R⁶ preferably or particularly have thesame meanings as given above within the framework of the definition ofsubstituents for formula (I) as being preferred or particularlypreferred respectively, and X¹ and X² preferably and particularlypreferably represent chlorine.

The following may be mentioned as starting materials of the formulae(IV) and (V): 2-chloro-, 2-fluoro-, 2-bromo-, 2-nitro-, 2-methyl-,2-methoxycarbonyl-, 2-ethoxycarbonyl-, 2-methoxy-, 2-ethoxy-, 2-phenyl-,2-trifluoromethyl-, 2-difluoromethoxy-, 2-trifluoromethoxy-, 2-phenoxy-,2-methyl-5-chloro-, 2,5-dichloro- and2-chloro-5-trifluoromethyl-benzenesulphonyl chloride and thecorresponding sulphenyl and sulphinyl chlorides.

Halogen/sulphur compounds of the formulae (IV) and (V) are known (seeChemistry Lett. 1978, 951; EP-PA Nos. 23,422, 35,893, 42,731, 44,808,44,809, 51,466, 64,804 and 70,041; U.S. Pat. Nos. 2,929,820, 4,282,242and 4,372,778; and J. Org. Chem. 33 (1968), 2104).

The compounds of the formulae (IV) and (V), in which m and nrespectively represent the number 2, are essentially obtained by the twofollowing methods of synthesis:

(b¹)

by reacting the corresponding sulphonic acids R⁵ --SO₃ H or R⁶ --SO₃ Hor their alkali metal or alkaline earth metal salts with halogenatingagents, such as, for example, phosphorus(V) chloride (phosphoruspentachloride), phosphoryl chloride (phosphoroxychloride), thionylchloride, phosgene or benzotrichloride, if appropriate in the presenceof catalysts, such as, for example, pyridine or dimethylformamide, and,if appropriate, using inert diluents, such as, for example, methylenechloride, chloroform, acetonitrile, chlorobenzene and/or sulphonlane, attemperatures between -20° C. and +150° C., preferably between 0° C. and+100° C., after dilution with water, the sulphonyl chlorides--if theyare obtained in crystalline form--can be isolated by filtration undersuction or can be purified by extraction with a water-immisciblesolvent, such as, for example, methylene chloride, diethyl ether orhexane, washing and drying of the extracts, evaporating down andrecrystallization or distillation; or

(b²)

in the case in which X¹ and X² represent chlorine and R⁵ and R⁶represent an aromatic radical, in a manner which is known in itself (seeJ. Org. Chem. 25 (1960), 1824; DE-OS (German Published Specification)No. 2,308,262 and EP-PA No. 59,241) by reacting appropriate aminocompounds R⁵ --NH₂ and R⁶ --NH₂ respectively with sodium nitrite andhydrochloric acid, if appropriate in the presence of acetic acid, attemperatures between -10° C. and +20° C., preferably between -5° C. and+10° C., and then (in situ) with sulphur dioxide or a salt of sulphurousacid, such as, for example, sodium sulphite or sodium bisulphite, in thepresence of a copper compound, such as, for example, copper chloride orcopper sulphate, as a catalyst, at temperatures between 0° C. and 80°C., preferably between 10° C. and 60° C.

Working up can be carried out in a customary manner: on dilution withwater, the sulphonyl chlorides are obtained in general in crystallineform, and can be isolated by filtering them off under suction. However,they can also be extracted from the aqueous dispersion with a solventwhich is virtually water-immiscible, such as, for example, methylenechloride or diethyl ether, and can be dried, and purified by vacuumdistillation.

Formula (VI) gives a definition of the isothioureas to be used asstarting materials in process (c). In this formula, R¹⁵ preferablyrepresents C₁ -C₄ -alkyl or benzyl, in particular methyl, and R¹, R² andM preferably or particularly have the same meanings as given abovewithin the framework of the definition of substituents for formula (I)as being preferred or particularly preferred.

The following may be mentioned as examples of the starting materials ofthe formula (VI): N'-(4,6-dimethoxy-s-triazin-2-yl)-,N'-(4,6-dimethyl-pyrimidin-2-yl)-,N'-(4-methoxy-6-methyl-pyrimidin-2-yl)-,N'-(4-ethoxy-6-methyl-pyrimidin-2-yl)-,N'-(4-propoxy-6-methyl-pyrimidin-2-yl)-,N'-(4-isopropoxy-6-methyl-pyrimidin-2-yl)-,N'-(4-butoxy-6-methyl-pyrimidin-2-yl)-,N'-(4-isobutoxy-6-methyl-pyrimidin-2-yl)-,N'-(4,6-dimethoxy-pyrimidin-2-yl)-, N'-(4,6-dimethyl-s-triazin-2-yl)-,N'-(4-methoxy-6-methyl-s-triazin-2-yl)-,N'-(4-ethoxy-6-methyl-s-triazin-2-yl)-,N'-(4,5,6-trimethyl-pyrimidin-2-yl)- andN'-(5-chloro-4,6-dimethyl-pyrimidin-2-yl)-,-N"-(2-fluoro-benzenesulphonyl)-, -N"-(2-chloro-benzenesulphonyl)-,-N"-(2-bromo-benzenesulphonyl)-, -N"-(2-nitro-benzenesulphonyl)-,-N"-(2-methyl-benzenesulphonyl)-,-N"-(2-methoxycarbonyl-benzenesulphonyl)-,-N"-(2-ethoxycarbonyl-benzenesulphonyl)-,-N"-(2-methoxy-benzenesulphonyl)-, -N"-(2-ethoxy-benzenesulphonyl)-,-N"-(2-phenyl-benzenesulphonyl)-,-N"-(2-trifluoromethyl-benzenesulphonyl)-,-N"-(2-difluoromethoxy-benzenesulphonyl)-,-N"-(2-trifluoromethoxy-benzenesulphonyl)-,-N"-(2-phenoxy-benzenesulphonyl)-,-N"-(2-methyl-5-chloro-benzenesulphonyl)-,-N"-(2,5-dichloro-benzenesulphonyl)- and-N"-(2-chloro-5-trifluoromethyl-benzenesulphonyl)-S-methyl-isothiourea.

Isothioureas of the formula (VI) are known (see EP-PA No. 5,986). Thesecompounds are obtained in a manner which is in itself known, by reactingappropriate isodithiocarbamic acid derivatives of the formula (VIII)##STR51## in which

R¹ and R¹⁵ have the meanings given above, with amino-hetarenes of theformula (IX)

    M--NH--R.sup.2                                             (IX)

in which

M and R² have the meanings given above, if appropriate in the presenceof a base which is strong but slightly nucleophilic, such as, forexample, sodium hydride, and, if appropriate, in the presence of adiluent, such as, for example, tetrahydrofuran, dioxane,1,2-dimethoxyethane, dimethylformamide or dimethyl sulphoxide, attemperatures between -20° C. and 100° C., preferably between 0° C. and+80° C. Working up can be carried out by customary methods, for exampleby dilution with water and acidification, for example with hydrochloricacid, after which the products of the formula (VI), which are obtainedin crystalline form, can be isolated by filtration under suction.

Formula (VIII) gives a definition of the isodithiocarboxylic acidderivatives required as intermediate products. In this formula, R¹ andR¹⁵ preferably or particularly have the same meanings as given abovewithin the framework of the definition of substituents for formula (I)or (VI) as being preferred or particularly preferred.

The following may be mentioned as examples of the compounds of theformula (VIII): N-(2-fluoro-benzenesulphonyl),N-(2-chloro-benzenesulphonyl), N-(2-bromo-benzenesulphonyl),N-(2-nitro-benzenesulphonyl), N-(2-methyl-benzenesulphonyl),N-(2-methoxycarbonyl-benzenesulphonyl),N-(2-ethoxycarbonyl-benzenesulphonyl), N-(2-methoxy-benzenesulphonyl),N-(2-ethoxy-benzenesulphonyl), N-(2-phenyl-benzenesulphonyl),N-(2-difluoromethoxy-benzenesulphonyl),N-(2-trifluoromethoxy-benzenesulphonyl), N-(2-phenoxy-benzenesulphonyl),N-(2-methyl-5-chloro-benzenesulphonyl),N-(2,5-dichloro-benzenesulphonyl) andN-(2-chloro-5-trifluoromethyl-benzenesulphonyl) S',S"-dimethylisodithiocarbamate.

The isodithiocarbamic acid derivatives of the formula (VIII) largelyhave not yet been described in the literature. These compounds areobtained in a manner which is in itself known (see Chem. Ber. 99 (1966),2885) by reacting amino compounds of the formula (X)

    R.sup.1 --NH.sub.2                                         (X)

in which

R¹ has the meaning given above, with carbon disulphide in the presenceof a strong base, such as, for example, sodium hydroxide, and, ifappropriate, in the presence of diluents, such as, for example, waterand dimethylformamide, at temperatures between -20° C. and +150° C.,preferably between 0° C. and 100° C., followed by reaction (in situ)with an alkylating agent of the formula (XI)

    Hal.sup.2 --R.sup.15                                       (XI)

in which

R¹⁵ has the meaning given above and

Hal² represents chlorine, bromine or iodine, at temperatures between-20° C. and +150° C., preferably between 0° C. and 100° C.

The products of the formula (VIII), which are obtained in crystallineform after dilution with water, can be isolated by filtration undersuction.

In formula (X), R¹ preferably or particularly has the same meaning asgiven above within the framework of the definition o substituents forformula (I) as being preferred or particularly preferred.

The following may be mentioned as examples of the compounds of theformula (X): 2-fluoro-, 2-chloro-, 2-bromo-, 2-nitro-, 2-methyl-,2-methoxycarbonyl-, 2-ethoxycarbonyl-, 2-methoxy-, 2-ethoxy-, 2-phenyl-,2-difluoromethoxy-, 2-trifluoromethoxy-, 2-phenoxy-, 2-methyl-5-chloro-,2,5-dichloro- and 2-chloro-5-trifluoromethyl-benzenesulphonamide.

Some of the amino compounds of the formula (X) are known (see EP-PA Nos.23,422, 30,140, 35,893, 44,807, 44,808, 44,809, 51,466, 64,804, 70,041and 70,802; and U.S. Pat. No. 4,372,778).

These compounds are obtained in a manner which is in itself known, byreacting appropriate chlorine compounds R¹ --Cl with ammonia, ifappropriate using inert diluents, such as, for example, diethyl ether ortetrahydrofuran, at temperatures between -20° C. and +100° C.,preferably between 0° C. and 50° C. The products of the formula (X),which are obtained in crystalline form in this procedure, can beisolated by filtration under suction.

Examples of suitable precursors of the formula R¹ --Cl and methods ofpreparing these are given above in the description of the startingmaterials for process (b).

In formula (XI), R¹⁵ preferably represents C₁ -C₄ -alkyl or benzyl, inparticular methyl, and Hal² represents chlorine, bromine or iodine.

The following may be mentioned as examples of compounds of the formula(XI): methyl chloride, methyl bromide, methyl iodide, ethyl chloride,ethyl bromide and ethyl iodide, as well as benzyl chloride and benzylbromide.

The compounds of the formula (XI) are known.

Formula (IX) gives a definition of the aminohetarenes furthermore to beused as intermediate products. In this formula, R² preferably orparticularly represents the same radicals as given within the frameworkof the definition of substituents for formula (I) as being preferred orparticularly preferred, and M preferably represents hydrogen, sodium orpotassium or one equivalent of magnesium or calcium, in particularhydrogen.

The following may be mentioned as examples of the compounds of theformula (IX): 4,6-dimethyl-, 4,5,6-trimethyl-, 5-chloro-4,6-dimethyl-,4-methoxy-6-methyl-, 4-ethoxy-6-methyl-, 4-propoxy-6-methyl-,4-isopropoxy-6-methyl-, 4-butoxy-6-methyl-, 4-isobutoxy-6-methyl- and4,6-dimethoxy-2-amino-pyrimidine as well as 4,6-dimethyl-,4-methoxy-6-methyl-, 4-ethoxy-6-methyl- and4,6-dimethoxy-2-amino-s-triazine.

Compounds of the formula (IX) are known and can be prepared by processeswhich are in themselves known (see Chem. Phar. Bull. 11 (1963),1382-1388; and U.S. Pat. No. 4,299,960).

Formula (III) gives a definition of the amino compounds furthermore tobe used as starting materials in process (c) according to the invention.The preferred and particularly preferred meanings of the formula (III)are listed above within the framework of the description of the startingmaterials for process (a).

Formula (I) and the conditions stated above under (d) give generaldefinitions of the guanidine derivatives to be used as startingmaterials in process (d).

In formula (I)--where it relates to the guanidine derivatives to be usedas starting materials for process (d)--R¹ and R³ preferably representthe radicals --S(O)_(m) --R⁵ and --S(O)_(n) --R⁶ respectively, wherein mand n and R⁵ and R⁶ preferably or particularly have the same meanings asgiven above within the framework of the definition of substituents forformula (I) as being preferred or particularly preferred; furthermore,R², R⁴ and M preferably or particularly have the same meanings as givenabove within the framework of the definition of substituents for formula(I) as being preferred or particularly preferred.

The following may be mentioned as examples of the compounds of theformula (I) which are to be used as starting materials in process (d):N'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-chloro-benzenesulphonyl)-,-N",N"'-bis-(2-bromo-benzenesulphonyl)-,-N",N"'-bis-(2-fluoro-benzenesulphonyl)-,-N",N"'-bis-(2-methoxy-benzenesulphonyl)-,-N",N"'-bis-(2-methyl-benzenesulphonyl)- and-N",N"'-bis-(2-methoxycarbonyl-benzenesulphonyl)-guanidine.

The guanidine derivatives of the formula (I) which are to be used asstarting materials for process (d) have not been described in theliterature hitherto. They can be obtained by the preparation processesdescribed above under (b).

Formula (III) gives a definition of the amino compounds furthermore tobe used as starting materials in process (c) according to the invention.The preferred and particularly preferred meanings of R³ and R⁴, as wellas examples of compounds of the formula (III), are given above in thedescription of the starting materials for process (a).

Formula (I) and the conditions stated above under (c) give definitionsof the guanidine derivatives to be used as starting materials in process(e). In formula (I)--where it relates to guanidine derivatives to beused as starting materials for process (e)--M represents hydrogen andthe radicals R¹, R², R³ and R⁴ preferably or particularly have the samemeanings as given above within the framework of the definition ofsubstituents for formula (I) as being preferred or particularlypreferred.

The following may be mentioned as examples of compounds of the formula(I) which are to be used as starting materials in process (e):N'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-fluoro-benzenesulphonyl)-,-N",N"'-bis-(2-chloro-benzenesulphonyl)-,-N",N"'-bis-(2-bromo-benzenesulphonyl)-,-N",N"'-bis-(2-methoxy-benzenesulphonyl)-,-N",N"'-bis-(2-methyl-benzenesulphonyl)- and-N",N"'-bis-(2-methoxycarbonyl-benzenesulphonyl)-guanidine as well asN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-N"'-(2-fluoro-benzenesulphonyl)-,-N"',-(2-chloro-benzenesulphonyl)-, -N"'-(2-bromo-benzenesulphonyl)-,-N"'-(2-methyl-benzenesulphonyl)-, -N"'-(2-methoxy-benzenesulphonyl)-and -N"'-(2-methoxycarbonyl-benzenesulphonyl)-guanidine.

The guanidine derivatives of the formula (I) which are to be used asstarting materials for process (e) have not been described in theliterature hitherto. They can be obtained by the preparation processesdescribed above under (a), (b), (c) and (d).

The following may be mentioned as examples of metal hydroxides, hydridesor alkanolates or organometallic compounds which are to be used forprocess (e): lithium hydroxide, sodium hydroxide, potassium hydroxide,magnesium hydroxide and calcium hydroxide, lithium hydride, sodiumhydride and calcium hydride, sodium methylate and ethylate, potassiummethylate and ethylate and potassium tert.-butylate, as well asbutyl-lithium and isopropyl-magnesium chloride.

The following may be mentioned as examples of the amines which may, ifappropriate, be used in process (e): isopropylamine, diisopropylamine,isobutylamine, sec.-butylamine, tert.-butylamine, diisobutylamine,trimethylamine, triethylamine, dibenzylamine and ethyl-diisopropylamine.

Formula (I) gives a definition of the guanidine derivatives to be usedas starting materials in process (f). In formula (I), R¹, R², R³, R⁴ andM preferably or particularly have the same meanings as given abovewithin the framework of the definition of substituents for formula (I)as being preferred or particularly preferred. Examples of compounds ofthe formula (I), which can also be used as starting materials in process(f), are given above in the description of the starting materials forprocess (e).

In process (f), strong acids are employed as starting materials. Theseare preferably hydrohalic acids, such as hydrogen fluoride, hydrogenchloride, hydrogen bromide and hydrogen iodide, and furthermoresulphuric acid and phosphoric acid or alkanesulphonic acids which haveup to 4 carbon atoms and are optionally substituted by fluorine orchlorine, such as, for example, methanesulphonic acid, ethanesulphonicacid, chloromethanesulphonic acid, 2-chloroethanesulphonic acid andtrifluoromethanesulphonic acid, and also benzenesulphonic acid,p-toluenesulphonic acid, naphthalene-1-sulphonic acid,naphthalene-2-sulphonic acid, naphthalene-1,4-. -1,5-, -1,6-, -2,6- and-2,7-disulphonic acid. Hydrochloric acid (hydrogen chloride), sulphuricacid, benzenesulphonic acid and p-toluenesulphonic acid are particularlypreferred.

Process (a) is preferably carried out using diluents. Suitable diluentsare all inert organic solvents. Alcohols, such as, for example,methanol, ethanol, n- and iso-propanol, and n-, iso-, sec.- andtert.-butanol, are particularly suitable. Ethanol is particularlypreferred as the solvent.

Virtually all customarily used acid-binding agents can be employed asacid acceptors. These include, in particular, alkali metal and alkalineearth metal hydroxides, alkali metal and alkaline earth metalcarbonates, ammonia (if appropriate aqueous ammonia), and aliphatic,aromatic or heterocyclic amines, such as triethylamine,N,N-dimethylaniline, N,N-dimethyl-benzylamine, pyridine,diazabicyclooctane and diazabicycloundecene (DBU).

In pprocess (a), the reaction temperature can be varied within arelatively wide range. In general, the reaction is carried out atbetween 0° C. and 150° C., preferably between 20° C. and 120° C. Process(a) is generally carried out under atmospheric pressure.

To carry out process (a) according to the invention, in general between0.5 and 5 mols, preferably between 1 and 3 mols, of amino compound ofthe formula (III) or of its hydrochloride are employed per mol of cyanocompound of the formula (II).

The starting materials of the formulae (II) and (III) and, ifappropriate, the diluent are generally combined at room temperature orwith slight external cooling, and the reaction mixture is stirred, ifappropriate at elevated temperature, until the reaction is complete.

Working up and isolation of the new compounds of the formula (I) arecarried out by customary methods: the solution is diluted--ifappropriate after cooling and if appropriate after filtration--withwater, or is evaporated down in vacuo and the residue dissolved inwater, and the solution, if necessary after filtration, is brought, ifrequired, to a slightly alkaline pH value by adding one of theabovementioned acid acceptors. The products of the formula (I) areobtained in crystalline form in this procedure, and can be isolated byfiltration under suction.

Process (b) according to the invention, for the preparation of the newcompounds of the formula (I), is preferably carried out using diluents.

Suitable diluents are virtually all inert organic solvents, but aproticpolar solvents are preferred. These include optionally halogenatedhydrocarbons, such as, for example, methylene chloride, chloroform,toluene and chlorobenzene, nitriles, such as, for example, acetonitrileand propionitrile, dimethylformamide, dimethylacetamide, dimethylsulphoxide, sulpholane, hexamethylphosphoric acid triamide,1,2-dimethoxyethane, pyridine and 2-methyl-5-ethyl-pyridine.

Virtually all customarily used acid-binding agents can be employed asacid acceptors in process (b). These include, in particular, alkalimetal and alkaline earth metal hydroxides, alkali metal and alkalineearth metal hydrides, organometallic compounds, such as butyllithium,and also aliphatic, aromatic or heterocyclic amines, such astrimethylamine, triethylamine, N,N-dimethylaniline,N,N-dimethyl-benzylamine, diazabicyclooctane (DABCO),diazabicycloundecene (DBU), pyridine and 2-methyl-5-ethyl-pyridine.

In process (b), the reaction temperatures can be varied within arelatively wide range. In general, the reaction is carried out atbetween -80° C. and +100° C., preferably between -30° C. and +50° C.Process (b) according to the invention is carried out in general underatmospheric pressure.

In carry out process (b) according to the invention, in general between0.5 and 5 mols, preferably between 1 and 3 mols, of halogen/sulphurcompound of the formula (IV) and (V) are employed per mol of guanidineintermediate product of the formula (I).

The reaction components are usually combined at room temperature or withexternal cooling, and the reaction mixture is stirred until the reactionis complete.

Working up and isolation of the new compounds are carried out bycustomary methods: the mixture is shaken with water and awater-immiscible solvent, such as, for example, methylene chloride,chloroform or toluene, if appropriate after volatile components havebeen distilled off, and the organic phase is washed with water, dried,filtered and evaporated down. The products of the formula (I) whichremain in the residue are crystallised by digestion with organicsolvents, such as, for example, diethyl ether, ethyl acetate, ethanol orisopropanol, and if required are purified by recrystallization.

Process (c) according to the invention, for the preparation of compoundsof the formula (I), is preferably carried out using diluents. Suitablediluents are virtually all inert organic solvents. These include, inparticular, optionally chlorinated hydrocarbons, such as, for example,chloroform, carbon tetrachloride, toluene, xylene, chlorobenzene and1,2-dichlorobenzene, ethers, such as, for example, diisopropyl ether anddibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxyethane anddiglycol dimethyl ether (diglyme), nitriles, such as, for example,acetonitrile and propionitrile, as well as dimethylformamide,dimethylacetamide, dimethyl sulphoxide and sulpholane.

Acid-binding agents which have nucleophilic properties which do notcompete significantly with those of the amino compounds of the formula(III) are employed as acid acceptors in process (c). Examples of acidacceptors which may be mentioned are alkali metal and alkaline earthmetal carbonates, such as, for example, potassium carbonate and calciumcarbonate, tertiary amines, such as, for example, triethylamine,N,N-dimethylaniline and N,N-dimethylbenzylamine, as well as nitrogenheterocycles, such as, for example, pyridine, diazabicyclooctane (DABCO)and diazabicycloundecene (DBU).

In process (c), the reaction temperature can be varied within arelatively wide range. In general, the reaction is carried out atbetween 0° C. and 200° C., preferably between 20° C. and 120° C. Process(c) is carried out in general under atmospheric pressure.

To carry out process (c) according to the invention, in general between1 and 5 mols, preferably between 1 and 3 mols of amino compound of theformula (III) or its hydrochloride are employed per mol of isothourea ofthe formula (VI).

In general, the isothioureas of the formula (VI) and the diluent areinitially introduced at room temperature, and the amino compounds of theformula (III), or their hydrochlorides, and suitable acid acceptors aremetered in. The reaction mixture is then stirred, in general at anelevated temperature, until the reaction is complete. On cooling, theproducts of the formula (I) are usually obtained in crystalline form,and can be isolated by filtration under suction. If the products of theformula (I) are obtained in the form of ammonium salts, thecorresponding acids (M═H) can be prepared from these ammonium salts bydissolving them in water and acidifying the solution, for example withhydrochloric acid or sulphuric acid.

Process (d) according to the invention is preferably carried out usingdiluents. Suitable diluents are virtually all inert organic solventsand, where appropriate, also water. These include, in particular,alcohols, such as methanol, ethanol and n- and iso-propanol, ethers,such as tetrahydrofuran, dioxane and 1,2-dimethoxyethane, esters, suchas methyl acetate and ethyl acetate, nitriles, such as, for example,acetonitrile and propionitrile, and dimethylformamide and water.

Acid-binding agents which have nucleophilic properties which do notcompete significantly with those of the amino compounds of the formula(III) can be employed as acid acceptors in process (d).

Acid acceptors which may be mentioned are alkali metal and alkalineearth metal carbonates, such as, for example, potassium carbonate andcalcium carbonate, tertiary amines, such as, for example, triethylamine,N,N,dimethylaniline and N,N-dimethylbenzylamine, and nitrogenheterocycles, such as, for example, pyridine, diazabicyclooctane (DABCO)and diazabicycloundecene (DBU).

In process (d), the reaction temperature can be varied within arelatively wide range. In general, the reaction is carried out atbetween 0° C. and 150° C., preferably between 10° C. and 100° C. Process(d) is carried out in general under atmospheric pressure.

To carry out process (d) according to the invention, in general between1 and 10 mols, preferably between 2 and 5 mols, of amino compound of theformula (III) or its hydrochloride are employed per mol of guanidineintermediate product of the formula (I).

In general, the guanidine derivatives of the formula (I) and the diluentare initially introduced at room temperature or with slight cooling, andthe amino compound of the formula (III), or its hydrochloride, andsuitable acid acceptors are metered in. The reaction mixture is thenstirred, in general at room temperature or an elevated temperature,until the reaction is complete.

Working up can be carried out by customary methods. If the products ofthe formula (I) are obtained from the reaction mixture in crystallineform, they can be isolated by filtration under suction. Otherwise, themixture, if necessary after being evaporated down, is diluted with waterand extracted with a solvent which is virtually water-immiscible, suchas, for example, methylene chloride. By washing the extraction solutionwith water, drying, filtering, evaporating down the filtrate andrecrystallising the residue, the products of the formula (I) can beobtained in pure form.

Process (e) according to the invention is preferably carried out usingdiluents. Suitable diluents are virtually all inert organic solvents.These include, in particular, alcohols, such as, for example, ethanoland n- and iso-propanol, ethers, such as, for example, tetrahydrofuran,dioxane and 1,2-dimethoxyethane, esters, such as, for example, methylacetate and ethyl acetate, and nitriles, such as, for example,acetonitrile.

In process (e), the reaction temperature can be varied within arelatively wide range. In general, the reaction is carried out atbetween -20° C. and +50° C., preferably between 0° C. and 30° C. Process(e) is carried out in general under atmospheric pressure.

To carry out process (e) according to the invention, in general between0.9 and 1.2 mols, preferably between 0.95 and 1.1 mols, of metalcompound or amine are employed per mole of guanidine derivative of theformula (I).

In general, the guanidine derivatives of the formula (I) and the diluentare initially introduced and--if appropriate with slight externalcooling--the metal compound or the amine--if appropriate dissolved inthe diluent--is metered in. The reaction mixture is stirred until thereaction is complete. The salt-like products of the formula (I) areobtained in general in crystalline form, and can be isolated byfiltration under suction.

Process (f) according to the invention is preferably carried out usingdiluents. Suitable diluents are virtually all organic solvents. Theseinclude, in particular, alcohols, such as methanol, ethanol and n- andiso-propanol, ethers, such as tetrahydrofuran, dioxane and1,2-dimethoxyethane, and esters, such as methyl acetate and ethylacetate.

If the acids used as starting materials are employed in aqueoussolution, acetic anhydride can also advantageously be used as a diluent.

In process (f), the reaction temperature can be varied within arelatively wide range. In general, the reaction is carried out atbetween -20° C. and +50° C., preferably between 0° C. and 30° C. Process(f) is carried out in general under atmospheric pressure.

To carry out process (f) according to the invention, in general between1 and 10 mols, preferably between 1.5 and 5 mols, of a strong acid areemployed per mol of guanidine derivative of the formula (I).

In general, the guanidine derivatives of the formula (I) and the diluentare initially introduced and--if appropriate with slight externalcooling--the strong acid is metered in. The reaction mixture is stirreduntil the reaction is complete. The 1:1 adducts are obtained in generalin crystalline form, and can be isolated by filtration under suction.

The active compounds according to the invention influence plant growthand can therefore be used as defoliants, desiccants, agents fordestroying broad-leaved plants and germination inhibitors, andespecially as weedkillers, and also as plant growth regulators. Byweeds, in the broadest sense, there are to be understood all plantswhich grow in locations where they are undesired. Whether the substancesaccording to the invention act as total or selective herbicides or asplant growth regulators depends essentially on the amount used.

The active compounds according to the invention can be used, forexample, in connection with the following plants:

Dicotyledon weeds of the genera:

Sinapis, Lepidium, Galium, Stellaria, Matricaria, Anthemis, Galinsoga,Chenopodium, Urtica, Senecio, Amaranthus, Portulaca, Xanthium,Convolvulus, Ipomoea, Polygonum, Sesbania, Ambrosia, Cirsium, Carduus,Sonchus, Solanum, Rorippa, Rotala, Lindernia, Lamium, Veronica,Abutilon, Emex, Datura, Viola, Galeopsis, Papaver and Centaurea.

Dicotyledon cultures of the genera:

Gossypium, Glycine, Beta, Daucus, Phaseolus, Pisum, Solanum, Linum,Ipomoea, Vicia, Nicotiana, Lycopersicon, Arachis, Brassica, Lactuca,Cucumis and Cucurbita.

Monocotyledon weeds of the genera:

Echinochloa, Setaria, Panicum, Digitaria, Phleum, Poa, Festuca,Eleusine, Brachiaria, Lolium, Bromus, Avena, Cyperus, Sorghum,Agropyron, Cynodon, Monochoria, Fimbristylis, Sagittaria, Eleocharis,Scirpus, Paspalum, Ischaemum, Sphenoclea, Dactyloctenium, Agrostis,Alopecurus and Apera.

Monocotyledon cultures on the genera:

Oryza, Zea, Triticum, Hordeum, Avena, Secale, Sorghum, Panicum,Saccharum, Ananas, Asparagus and Allium.

However, the use of the active compounds according to the invention isin no way restricted to these genera, but also extends in the samemanner to other plants.

The compounds are suitable, depending on the concentration; for thetotal combating of weeds, for example on industrial terrain and railtracks, and on paths and squares with or without tree plantings.Equally, the compounds can be employed for combating weeds in perennialcultures, for example afforestations, decorative tree plantings,orchards, vineyards, citrus groves, nut orchards, banana plantations,coffee plantations, tea plantations, rubber plantations, oil palmplantations, cocoa plantations, soft fruit plantings and hopfields, andfor the selective combating of weeds in annual cultures.

The active compounds according to the invention also engage in themetabolism of the plants and, as already mentioned, can therefore beemployed as growth regulators, with certain preconditions.

Experience to date of the mode of action of plant growth regulators hasshown that an active compound can also exert several different actionson plants. The actions of the compounds depend essentially on the pointin time at which they are used, relative to the stage of development ofthe plant, and on the amounts of active compound applied to the plantsor their environment and the way in which the compounds are applied. Inevery case, growth regulators are intended to influence the crop plantsin the particular manner desired.

Plant growth regulating compounds can be employed, for example, toinhibit vegetative growth of the plants. Such inhibition of growth isinter alia of economic interest in the case of grasses, since it isthereby possible to reduce the frequency of cutting the grass inornamental gardens, parks and sportsgrounds, at verges, at airports orin fruit orchards. The inhibition of growth of herbaceous and woodyplants at verges and in the vicinity of pipelines or overland lines or,quite generally, in areas in which heavy additional growth of plants isundesired, is also of importance.

The use of growth regulators to inhibit the growth in length of cerealsis also important. The danger of lodging of the plants before harvestingis thereby reduced or completely eliminated. Furthermore, growthregulators can strengthen the stem of cereals, which again counteractslodging. Use of growth regulators for shortening and strengthening thestem enables higher amounts of fertiliser to be applied to increase theyield, without danger of the cereal lodging.

In the case of many crop plants, inhibition of the vegetative growthmakes denser planting possible, so that greater yields per area ofground can be achieved. An advantage of the smaller plants thus producedis also that the crop can be worked and harvested more easily.

Inhibition of the vegetative growth of plants can also lead to increasesin yield, since the nutrients and assimilates benefit blossoming andfruit formation to a greater extent than they benefit the vegetativeparts of plants.

Promotion of vegetative growth can also frequently be achieved withgrowth regulators. This is of great utility if it is the vegetativeparts of the plants which are harvested. Promoting the vegetative growthcan, however, also simultaneously lead to a promotion of generativegrowth, since more assimilates are formed, so that more fruit, or largerfruit, is obtained.

Increases in yield can in some cases be achieved by affecting the plantmetabolism, without noticeable changes in vegetative growth. A change inthe composition of plants, which in turn can lead to a better quality ofthe harvested products, can furthermore be achieved with growthregulators. Thus it is possible, for example, to increase the content ofsugar in sugar beet, sugar cane, pineapples and citrus fruit or toincrease the protein content in soya beans or cereals. Using growthregulators it is also possible, for example, to inhibit the degradationof desired constituents, such as, for example, sugar in sugar beet orsugar cane, before or after harvesting. It is also possible favourablyto influence the production or the efflux of secondary plantconstituents. The stimulation of latex flux in rubber trees may bementioned as an example.

Parthenocarpous fruit can be formed under the influence of growthregulators. Furthermore, the gender of the flowers can be influenced.Sterility of the pollen can also be produced, which is of greatimportance in the breeding and preparation of hybrid seed.

Branching of plants can be controlled by using growth regulators. On theone hand, by breaking the apical dominance the development of sideshoots can be promoted, which can be very desirable, especially in thecultivation or ornamental plants, also in connection with growthinhibition. On the other hand, however, it is also possible to inhibitthe growth of side shoots. There is great interest in this action, forexample, in the cultivation of tobacco or in the planting of tomatoes.

The amount of leaf on plants can be controlled under the influence ofgrowth regulators, so that defoliation of the plants at a desired pointin time is achieved. Such defoliation is of great importance in themechanical harvesting of cotton, but is also of interest forfacilitating harvesting in other crops, such as, for example, inviticulture. Defoliation of the plants can also be carried out to lowerthe transpiration of plants before they are transplanted.

The shedding of fruit can also be controlled with growth regulators. Onthe one hand, it is possible to prevent premature shedding of fruit.However, on the other hand, shedding of fruit, or even the fall ofblossom, can be promoted up to a certain degree (thinning out) in orderto interrupt the alternance. By alternance there is understood thepeculiarity of some varieties of fruit to produce very different yieldsfrom year to year, for endogenic reasons. Finally, using growthregulators it is possible to reduce the force required to detach thefruit at harvest time so as to permit mechanical harvesting orfacilitate manual harvesting.

Using growth regulators, it is furthermore possible to achieve anacceleration or retardation of ripening of the harvest product, beforeor after harvesting. This is of particular advantage, since it isthereby possible to achieve optimum adaptation to market requirements.Furthermore, growth regulators can at times improve the coloration offruit. In addition, concentrating the ripening within a certain periodof time is also achievable with the aid of growth regulators. Thisprovides the preconditions for being able to carry out completemechanical or manual harvesting in only a single pass, for example inthe case of tobacco, tomatoes or coffee.

Using growth regulators, it is furthermore possible to influence thelatent period of seeds or buds of plants, so that the plants, such as,for example, pineapple or ornamental plants in nurseries, germinate,shoot or blossom at a time at which they normally show no readiness todo so. Retarding the shooting of buds or the germination of seeds withthe aid of growth regulators can be desirable in regions where frost isa hazard, in order to avoid damage by late frosts.

Finally, the resistance of plants to frost, drought or a high saltcontent in the soil can be induced with growth regulators. Cultivationof plants in regions which are usually unsuitable for this purposethereby becomes possible.

The active compounds can be converted to the customary formulations,such as solutions, emulsions, suspensions, powders, foams, pastes,granules, aerosols, very fine capsules in polymeric substances and incoating compositions for seed, as well as ULV formulations.

These formulations are produced in known manner, for example by mixingthe active compounds with extenders, that is, liquid solvents, liquefiedgases under pressure, and/or solid carriers, optionally with the use ofsurface-active agents, that is, emulsifying agents and/or dispersingagents, and/or foam-forming agents. In the case of the use of water asan extender, organic solvents can, for example, also be used asauxiliary solvents. As liquid solvents, there are suitable in the main:aromatics, such as xylene, toluene or alkyl naphthalenes, chlorinatedaromatics or chlorinated aliphatic hydrocarbons, such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons, such ascyclohexane or paraffins, for example mineral oil fractions, alcohols,such as butanol or glycol as well as their ethers and esters, ketones,such as acetone, methyl ethyl ketone, methyl isobutyl ketone orcyclohexanone, strongly polar solvents, such as dimethylformamide anddimethylsulphoxide, as well as water. By liquefied gaseous extenders orcarriers are meant liquids which are gaseous at normal temperature andunder normal pressure, for example aerosol propellants, such ashalogenated hydrocarbons as well as butane, propane, nitrogen and carbondioxide. As solid carriers there are suitable: for example, groundnatural minerals, such as kaolins, clays, talc, chalk, quartz,attapulgite, montmorillonite or diatomaceous earth, and ground syntheticminerals, such as highly dispersed silicic acid, alumina and silicates.As solid carriers for granules there are suitable: for example, crushedand fractionated natural rocks such as calcite, marble, pumice,sepiolite and dolomite, as well as synthetic granules of inorganic andorganic meals, and granules of organic material such as sawdust, coconutshells, corn cobs and tobacco stalks. As emulsifying and/or foam-formingagents there are suitable: for example, non-ionic and anionicemulsifiers, such as polyoxyethylene-fatty acid esters,polyoxyethylene-fatty alcohol ethers, for example alkylaryl polyglycolethers; alkylsulphonates, alkylsulphates, arylsulphonates as well asalbumin hydrolysis products. As dispersing agents there are suitable:for example, lignin-sulphite waste liquors and methylcellulose.

Adhesives such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or latices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, can be used in theformulations.

It is possible to use dyestuffs such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations in general contain between 0.1 and 95 percent by weightof active compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be present in theformulations as a mixture with other known active compounds, such asfungicides, insecticides, acaricides and herbicides, and also asmixtures with fertilizers and other growth regulators.

Suitable herbicides for the mixtures are known herbicides, such as, forexample,1-amino-6-ethylthio-3-(2,2-dimethylpropyl)-1,3,5-triazine-2,4(1H,3H)-dioneor N-(2-benzothiazolyl)-N,N'-dimethyl-urea for combating weeds incereals; 4-amino-3-methyl-6-phenyl-1,2,4-triazin-5(4H)-one for combatingweeds in sugar beet and4-amino-6-(1,1-dimethylethyl)-3-methylthio-1,2,4-triazin-5(4H)-one forcombating weeds in soybeans. Surprisingly, some mixtures also have asynergistic effect.

The active compounds can be used as such, in the form of theirformulations or as the use forms prepared therefrom, such asready-to-use solutions, emulsifiable concentrates, emulsions, foams,suspensions, wettable powders, pastes, soluble powders, dusting agentsand granules. They are used in the customary manner, for example bywatering, spraying, atomizing, scattering, dusting, foaming, coating andthe like. Furthermore, it is possible to apply the active compounds inaccordance with the ultra-low volume process or to inject the activecompound preparation or the active compound itself into the soil. It isalso possible to treat the seeds of plants.

The active compounds according to the invention can be applied before aswell as after emergence of the plants. They are preferably appliedbefore emergence of the plants, that is to say by the pre-emergencemethod. They can also be incorporated into the soil before sowing.

The amount of active compound applied can vary within a substantialrange. It depends essentially on the type of effect desired. In general,the amounts applied are between 0.001 and 10 kg of active compound perha, preferably between 0.01 and 5 kg/ha.

As regards the time of application, the rule is that the growthregulators are applied within a preferred period of time, the exactdefinition of which depends on the climatic and vegetativecircumstances.

The examples which follow serve to illustrate the invention further.

PREPARATION EXAMPLES EXAMPLE 1 ##STR52##

(Process a)

A mixture of 109 g (0.67 mol) of 0-methylhydroxylamine hydrochloride, 99g (0.67 mol) of 2-cyanoamino-4,6-dimethylpyrimidine and 600 ml ofethanol is heated at the boil under reflux for 7 hours. Thereafter, thealcohol is distilled off in the vacuum from a water jet, the residue isdissolved in hot water, and 100 ml of concentrated ammonia are added tothis solution. The product which crystallizes out is filtered off undersuction and recrystallized from ethanol.

71.8 g (55% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-guanidine of melting point134° C. to 136° C. are obtained.

EXAMPLE 2 ##STR53##

(Process a)

A mixture of 7.7 g (0.06 mol) of 4-chloroaniline hydrochloride, 7.4 g(0.05 mol) of 2-cyanoamino-4,6-dimethyl-pyrimidine and 150 ml of ethanolis heated at the boil under reflux for 15 hours. After cooling, thereaction mixture is diluted with 150 ml of water, and is renderedalkaline with 2N sodium hydroxide solution. The product whichcrystallizes out is filtered off under suction.

8.3 g (60% of theory) ofN'-(4,6-dimethylpyrimidin-2-yl)-N"-(4-chlorophenyl)-guanidine of meltingpoint 203° C. are obtained.

EXAMPLE 3 ##STR54##

(Process a)

45 g (0.65 mol) of n-butylamine are added dropwise to a solution of 45 g(0.3 mol) of 2-cyanoamino-4,6-dimethyl-pyrimidine in 300 ml of ethanol,and the mixture is heated at the boil under reflux for 15 hours. Aftercooling, the mixture is filtered, and about 1.5 liters of water areadded to the filtrate. The product which crystallizes out is filteredoff under suction.

59.5 g (96% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-butyl-guanidine of melting point185° C. are obtained.

EXAMPLE 4 ##STR55##

(Process b)

A mixture of 29.4 g (0.15 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-guanidine, 63.6 g (0.3 mol)of 2-chloro-benzenesulphonyl chloride and 150 ml of pyridine is stirredfor 2 days at 20° C. After the pyridine has been substantially distilledoff in the vacuum from a water jet, 200 ml of water are added to theresidue and the mixture is extracted with 200 ml of methylene chloride.The organic phase is separated off, dried and evaporated down. Theresidue is brought to crystallization by digestion with ethanol.

41.2 g (51% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-chlorobenzenesulphonyl)-guanidineof melting point 164° C. to 166° C. are obtained.

The above structural formula applies to the crystalline state, and isconfirmed by X-ray structure analysis. Other spectroscopic data (IR, ¹H- and ¹³ C-NMR) and elemental analysis support the assignment of thisstructure.

EXAMPLE 5 ##STR56##

(Process b)

113 g (0.48 mol) of 2-methoxycarbonyl-benzenesulphonyl chloride areadded to a mixture, cooled to -10° C. of 35.1 g (0.18 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-guanidine and 160 ml ofpyridine, and the reaction mixture is stirred for two days at 20° C.After the pyridine has been substantially distilled off in the vacuumfrom a water jet, 200 ml of water are added to the residue and themixture is extracted with 200 ml of methylene chloride. The organicphase is separated off, dried with sodium sulphate, filtered andevaporated down. The residue is brought to crystallization by digestionwith isopropanol.

59 g (55% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-methoxycarbonylbenzenesulphonyl)-guanidineof melting point 165° C. are obtained.

The above structural formula applies to the crystalline state, and isconfirmed by X-ray structure analysis. Other spectroscopic data (IR, ¹H- and ¹³ C-NMR) and elemental analysis support the assignment of thisstructure.

EXAMPLE 6 ##STR57##

(Process b)

21.2 g (0.1 mol) of 2-chloro-benzenesulphonyl chloride are addeddropwise to a mixture of 12.1 g (0.05 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-phenyl-guanidine, 10.5 g (0.1 mol)of triethylamine and 100 ml of chloroform at 20° C., and the reactionmixture is stirred for 15 hours at 20° C. Thereafter, the reactionmixture is shaken with water, and the organic phase is separated off andevaporated down. The residue is suspended in ethanol, the suspension isfiltered, the filtrate is evaporated down and the residue is brought tocrystallization by digestion with ethyl acetate.

6.6 g (22% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-phenyl-N",N"'-bis-(2-chloro-benzenesulphonyl)-guanidineof melting point 120° C. are obtained.

EXAMPLE 7a ##STR58## and EXAMPLE 7b ##STR59##

(Process b)

12.2 g (0.05 mol) of 2,5-dichloro-benzenesulphonyl chloride are added toa mixture of 12.1 g (0.05 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-phenyl-guanidine, 5.1 g (0.05 mol)of triethylamine and 150 ml of chloroform at 0° C. to 10° C., and thereaction mixture is stirred for 15 hours at 20° C. Thereafter, thereaction mixture is washed with 100 ml of 5% strength hydrochloric acidand is evaporated down, the residue is digested with ethanol, and theproduct is filtered off under suction.

3.5 g (16% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-phenyl-N"'-(2,5-dichloro-benzenesulphonyl)-guanidine(7a) of melting point 188° C. are obtained.

The product which gradually crystallizes out from the mother liquor isisolated after a few days by filtering it off under suction. 1.8 g (8%of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-phenyl-N"-(2,5-dichloro-benzenesulphonyl)-guanidine(7b) of melting point 153° C. are obtained.

EXAMPLE 8 ##STR60##

(Process b)

1.6 g (0.055 mol) of 80% strength sodium hydride are added in portionsto a solution of 14.3 g (0.05 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-(4-nitrophenyl)-guanidine in 150 mlof dimethylformamide at 20° C. to 30° C., and the mixture is stirred for15 hours at 20° C. Thereafter, 10.6 g (0.05 mol) of2-chloro-benzenesulphonyl chloride are added dropwise, and the reactionmixture is stirred for 15 hours at 20° C. Thereafter, 500 ml of 5%strength hydrochloric acid are added. The product, which is obtained incrystalline form, is filtered off under suction.

9.4 g (41% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-(4-nitrophenyl)-N"'-(2-chloro-benzenesulphonyl)-guanidineof melting point 220° C. are obtained.

EXAMPLE 9 ##STR61##

(Process b)

5.3 g (0.025 mol) of 2-chloro-benzenesulphonyl chloride are addeddropwise to a mixture of 7.3 g (0.025 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N",N"'-dibutyl-guanidine and 5.3 g(0.05 mol) of triethylamine at 20° C. The reaction mixture is stirredfor 15 hours at 20° C., and is then washed with 100 ml of 5% strengthhydrochloric acid and evaporated down. The residue is brought tocrystallization by digestion with ethanol.

1.8 g (16% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N",N"'-dibutyl-N"'-(2-chloro-benzenesulphonyl)-guanidineof melting point 150° C. are obtained.

EXAMPLE 10a ##STR62## and EXAMPLE 10b ##STR63##

(Process c)

4.5 g (0.1 mol) of dimethylamine are passed into a mixture of 15 g(0.037 mol) ofN'-(4,6-dimethoxy-s-triazin-2-yl)-N"-(2-chloro-benzenesulphonyl)-S-methylisothioureaand 100 ml of dioxane at 25° C. to 35° C. The reaction mixture is thenstirred for one hour at 80° C. After the reaction mixture has cooled,the product, which is obtained in crystalline form, is isolated byfiltering it off under suction.

12.1 g (73% of theory) of the dimethyl-ammonium salt ofN'-(4,6-dimethoxy-s-triazin-2-yl)-N",N"'-dimethyl-N"'-(2-chloro-benzenesulphonyl)-guanidine(10a) of melting point 162° C. are obtained.

The ammonium salt (10a) is dissolved in 20 ml of water, and the solutionis acidified with concentrated hydrochloric acid. The product obtainedin crystalline form in this procedure is isolated by filtering it offunder suction.

4 g (28% of theory) ofN'-(4,6-dimethoxy-s-triazin-2-yl)-N",N"'-dimethyl-N"'-(2-chloro-benzenesulphonyl)-guanidine(10b) of melting point 185° C. are obtained.

EXAMPLE 11 ##STR64##

(Process d)

A mixture of 5.5 g (0.01 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-chloro-benzenesulphonyl)-guanidine(4), 1.5 g (0.025 mole) of N,N-dimethylhydrazine, 20 ml of ethanol and10 ml of water is heated at the boil under reflux for 15 minutes. Afterthe mixture has cooled, the product, which is obtained in crystallineform, is isolated by filtering it off under suction.

2.5 g (65% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-dimethylamino-N"'-(2-chloro-benzenesulphonyl)-guanidineof melting point 176° C. are obtained.

EXAMPLE 12 ##STR65##

(Process d)

A mixture of 5.5 g (0.01 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-chloro-benzenesulphonyl)-guanidine(4), 2.1 g of hydroxylamine hydrochloride (0.03 mol), 30 ml of ethanoland 5 ml of water, as well as 3.0 g (0.03 mol) of triethylamine, arestirred for 6 hours at 20° C. The product, which is obtained incrystalline form, is isolated by filtering it off under suction.

2.7 g (76% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-hydroxy-N"'-(2-chloro-benzenesulphonyl)-guanidineof melting point 139° C. are obtained.

EXAMPLE 13 ##STR66##

(Process e)

A solution of 0.9 g (0.01 mol) of potassium ethylate in 15 ml of ethanolis added to a mixture of 3.5 g (0.01 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methyl-N"'-(2-chloro-benzenesulphonyl)-guanidineand 15 ml of ethanol, and the reaction mixture is stirred for 3 hours at20° C. The product, which is obtained in crystalline form, is isolatedby filtering it off under suction.

3.8 g (96% of theory) of the potassium salt ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methyl-N"'-(2-chloro-benzenesulphonyl)-guanidineof melting point 290° C. are obtained.

EXAMPLE 14 ##STR67##

(Process f)

5 ml of concentrated hydrochloric acid (0.05 mol) are added to a mixtureof 5.5 g (0.01 mol) ofN'-(4,6-dimethylpyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-chloro-benzenesulphonyl)-guanidineand 25 ml of acetic anhydride at 20° C. (exothermic reaction!), and thereaction mixture is stirred for 2 hours. The product, which is obtainedin crystalline form, is isolated by filtering it off under suction.

4.3 g (74% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-N",N"'-bis-(2-chloro-benzenesulphonyl)-guanidinehydrochloride of melting point 142° C. are obtained.

EXAMPLE 15 ##STR68##

(Process f)

A mixture of 3.5 g (0.01 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methyl-N"'-(2-chloro-benzenesulphonyl)-guanidine,25 ml of isopropanol and 4.9 g (0.05 mol) of concentrated sulphuric acidis stirred for 6 hours at 20° C. The product, which is obtained incrystalline form, is isolated by filtering it off under suction.

3.1 g (64% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methyl-N"'-(2-chloro-benzenesulphonyl)-guanidinedihydrogen sulphate of melting point 162° C. are obtained.

It was possible to prepare the compounds of the formula (I) listed inthe table below by the processes described, by way of example, in theexamples above. ##STR69## PG,95

A few further derivatives of process (b) according to the invention aredescribed below by way of example:

Preparation of the compound ##STR70## listed above as Example (147).

10.6 g (0.05 mol) of 2-chloro-benzenesulphonyl chloride are addeddropwise to a mixture, cooled to -7° C., of 4.9 g (0.025 mol) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-methoxy-guanidine and 50 ml ofpyridine.

After the reaction mixture has been stirred for 10 minutes at -7° C.,400 ml of water are added to it. The product, which is obtained incrystalline form, is isolated by filtering it off under suction.

5.2 g (56% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-(2-chloro-benzenesulphonyl)-N"-methoxy-guanidineof melting point 90° C. are obtained.

Preparation of the compounds ##STR71## and ##STR72## listed above asExamples (35) and (6).

10.6 g (0.05 mol) of 2-chloro-benzenesulphonyl chloride are addeddropwise to a mixture of 9.3 g (0.05 mol) of tributylamine, 6.1 g (0.025mol) of N'-(4,6-dimethyl-pyrimidin-2-yl)-N"-phenyl-guanidine and 60 mlof cyclohexane at 30° C. After the mixture has been stirred for 15 hoursat 25° C., it is evaporated down, and the residue is triturated with 50ml of ethanol. The product, which is obtained in crystalline form, isisolated by filtering it off under suction.

1.4 g (13% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-phenyl-N"'-(2-chloro-benzenesulphonyl)-guanidine(35) of melting point 196° C. are obtained.

400 ml of water and 10 ml of concentrated hydrochloric acid are added tothe mother liquor. The crystalline product which forms during thisprocedure is isolated by filtering it off under suction.

5.0 g (34% of theory) ofN'-(4,6-dimethyl-pyrimidin-2-yl)-N"-phenyl-N",N"'-bis-(2-chloro-benzenesulphonyl)-guanidine(6) of melting point 120° C. are obtained.

The following acid adducts of compounds of the formula (I) werefurthermore obtained analogously to Example 15:

(5a) 1:1 adduct of Example (5) with sulphuric acid

(4a) 1:1 adduct of Example (4) with p-toluenesulphonic acid

(103a) 1:1 adduct of Example (103) with sulphuric acid

EXAMPLES OF THE PREPARATION OF THE STARTING MATERIALS OF THE FORMULA(II) ##STR73##

(Process (a¹))

52.7 g (0.3 mol) of 2-chloro-4,6-dimethoxy-s-triazine are added to asolution of 30 g (0.3 mol) of disodium cyanamide in 600 ml of acetone,and the reaction mixture is heated at the boil under reflux for 6 hours.After the solvent has been distilled off, the crystalline residue isdissolved in 250 ml of water and the solution is acidified withconcentrated hydrochloric acid. The product, which is obtained incrystalline form, is isolated by filtering it off under suction.

33 g (61% of theory) of 2-cyanoamino-4,6-dimethoxy-s-triazine having amelting point above 300° C. are obtained. ##STR74##

(Process (a²))

A mixture of 42 g (0.5 mol) of cyanoguanidine ("dicyanodiamide") and 50g (0.5 mol) of 2,4-pentanedione ("acetylacetone") is heated to 120° C.for 15 hours. The reaction mixture is then cooled, after which 500 ml ofwater are added and the solution is acidified with hydrochloric acid at0° C. to 10° C. The product obtained in crystalline form during thisprocedure is isolated by filtering it off under suction. 51.8 g (70% oftheory) of 2-cyanoamino-4,6-dimethyl-pyrimidine of melting point 205° C.are obtained.

It was possible to prepare the compounds of the formula (II) listedbelow in the same manner: ##STR75##

2-(Alkyl-cyano-amino)-pyrimidines of the formula (II) can be prepared,for example, as follows: ##STR76##

12.6 g (0.1 mol) of dimethyl sulphate are added dropwise to a solutionof 15 g (0.1 mol) of2-cyanoamino-4-hydroxy-6-methyl-pyrimidine--prepared by process(a²)--and 4.1 g (0.1 mol) of sodium hydroxide in 60 ml of water, thereaction temperature increasing from 20° C. to 40° C. After the mixturehas been stirred for two hours at 20° C., the product, which is obtainedin crystalline form, is isolated by filtering it off under suction.

11.1 g (68% of theory) of2-(methyl-cyano-amino)-4-hydroxy-6-methyl-pyrimidine of melting point290° C. are obtained.

The following compound is obtained analogously: ##STR77## M.p. 215° C.to 220° C. ##STR78##

127.5 g (1 mol) of dimethyl sulphate are added dropwise to a solution of75 g (0.5 mol) of 2-cyanoamino-4-hydroxy-6-methyl-pyrimidine--preparedby process (a²)--and 44 g (1.1 mols) of sodium hydroxide in 750 ml ofwater, the reaction temperature increasing from 20° C. to 35° C. Afterthe mixture has been stirred for twelve hours at 20° C., the pH value isadjusted to between 9 and 10 by the addition of sodium hydroxidesolution, and the product, which is obtained in crystalline form, isisolated by filtering it off under suction.

13 g (15% of theory) of2-(methyl-cyano-amino)-4-methoxy-6-methyl-pyrimidine of melting point123° C. are obtained.

The following compounds are obtained analogously: ##STR79##

EXAMPLES OF THE PREPARATION OF STARTING MATERIALS OF THE FORMULAE (IV)AND (V) ##STR80##

(Process (b¹))

295 ml of phosphoryl chloride ("phosphorus oxychloride") are addeddropwise, at 20° C. to 30° C., to a mixture of 172 g (0.8 mol) of sodium2-chloro-benzenesulphonate, 300 ml of acetonitrile and 300 ml ofsulpholane. The reaction mixture is stirred for 4 hours at 70° C., thencooled to 5° C. and diluted with ice-water. After the mixture has beenextracted with petroleum ether, and the extraction solution has beenwashed with water, dried, filtered and evaporated down, the productremaining in the residue is purified by vacuum distillation.

117 g (70% of theory) of 2-chloro-benzenesulphonyl chloride of boilingpoint 110° C./0.8 mm Hg are obtained.

In the same manner, it was possible to prepare the compounds of theformula (IV) which are listed below: ##STR81##

(Process (b²))

75.5 g (0.5 mol) of methyl 2-aminobenzoate are dissolved in 176 ml ofconcentrated hydrochloric acid and 100 ml of acetic acid. A solution of34.4 g of sodium nitrite in 70 ml of water is added dropwise to thissolution at 0° C. After the reaction mixture has been stirred for afurther 15 minutes, it is added slowly to a saturated solution, cooledto 0° C., the sulphur dioxide in 450 ml of acetic acid. After thecooling bath has been removed, the mixture is stirred until evolution ofgas is complete, 10 g of copper(II) chloride being introduced inportions. After the mixture has been diluted with ice-water andextracted with methylene chloride, and the extraction solution has beenwashed with water, dried, filtered and evaporated down, the productremaining in the residue is purified by vacuum distillation.

45 g (38% of theory) of 2-methoxy-carbonylbenzenesulphonyl chloride ofboiling point 150° C./1 mm Hg are obtained.

In the same manner, it was possible to prepare the compounds of theformula (IV) which are listed below: ##STR82##

EXAMPLES OF THE PREPARATION OF STARTING MATERIALS OF THE FORMULA (VI)##STR83##

11 g (0.4 mol) of sodium hydride (80% strength) are added in portions toa suspension of 31.2 g (0.2 mol) of 2-amino-4,6-dimethyl-s-triazine in200 ml of tetrahydrofuran at 20° C. After the mixture has been stirredfor 12 hours, 60 g (0.2 mol) of N-(2-chloro-benzenesulphonyl)S',S"-dimethyl isodithiocarbamate are added, the reaction temperatureincreasing to 60° C. The reaction mixture is stirred for 5 hours at 20°C., diluted with 800 ml of water and filtered. After acidification withconcentrated hydrochloric acid, the product crystallizes, and isisolated by filtering it off under suction.

42 g (48% of theory) ofN'-(4,6-dimethoxy-s-triazin-2-yl)-N"-(2-chloro-benzenesulphonyl)-S-methylisothioureaof melting point 176° C. are obtained.

In the same manner, it was possible to prepare the compounds of theformula (VI) which are listed below: ##STR84##

PREPARATION OF STARTING SUBSTANCES OF THE FORMULA (VI) EXAMPLE (VI-8)##STR85##

A suspension of 8.4 g (0.35 mole) of sodium hydride (in oil) is added toa mixture of 28.0 g (0.2 mole) of 2-amino-4-methoxy-6-methyl-pyrimidine,with stirring, and the mixture is stirred at 20° C. for 15 hours. 60 g(0.2 mole) of S',S"-dimethylN-(2-chloro-benzenesulphonyl)-imino-dithiocarbonate are then added inportions to the reaction mixture such that the reaction temperature doesnot rise above 40° C. After the mixture has been stirred at 20° C. for 5hours, 1 l of ice-water is added and the mixture is filtered. Thefiltrate is acidified with concentrated hydrochloric acid and theproduct thereby obtained as crystals is isolated by filtration withsuction.

67 g (87% of theory ofN'-(4-methoxy-6-methyl-pyrimidin-2-yl)-N"-(2-chloro-benzenesulphonyl)-S-methylisothioureaof melting point 148° C. are obtained.

The compounds of the formula (VI) listed in the following Table 2 can beprepared analogously:

                                      TABLE 2                                     __________________________________________________________________________     ##STR86##                                (VI)                                                                       Melting                                Example No.                                                                          R.sup.1      R.sup.2    R.sup.15                                                                           M  point (°C.)                     __________________________________________________________________________    VI-9                                                                                  ##STR87##                                                                                  ##STR88## CH.sub.3                                                                           H  163                                    VI-10                                                                                 ##STR89##                                                                                  ##STR90## CH.sub.3                                                                           H  163                                    VI-11                                                                                 ##STR91##                                                                                  ##STR92## CH.sub.3                                                                           H  168                                    VI-12                                                                                 ##STR93##                                                                                  ##STR94## CH.sub.3                                                                           H  152-153                                VI-13                                                                                 ##STR95##                                                                                  ##STR96## CH.sub.3                                                                           H                                         VI-14                                                                                 ##STR97##                                                                                  ##STR98## CH.sub.3                                                                           H                                         VI-15                                                                                 ##STR99##                                                                                  ##STR100##                                                                              CH.sub.3                                                                           H                                         VI-16                                                                                 ##STR101##                                                                                 ##STR102##                                                                              CH.sub.3                                                                           H                                         VI-17                                                                                 ##STR103##                                                                                 ##STR104##                                                                              CH.sub.3                                                                           H                                         VI-18                                                                                 ##STR105##                                                                                 ##STR106##                                                                              CH.sub.3                                                                           H                                         VI-19                                                                                 ##STR107##                                                                                 ##STR108##                                                                              CH.sub.3                                                                           H                                         VI-20                                                                                 ##STR109##                                                                                 ##STR110##                                                                              CH.sub.3                                                                           H                                         VI-21                                                                                 ##STR111##                                                                                 ##STR112##                                                                              CH.sub.3                                                                           H                                         VI-22                                                                                 ##STR113##                                                                                 ##STR114##                                                                              CH.sub.3                                                                           H                                         VI-23                                                                                 ##STR115##                                                                                 ##STR116##                                                                              CH.sub.3                                                                           H                                         VI-24                                                                                 ##STR117##                                                                                 ##STR118##                                                                              CH.sub.3                                                                           H                                         VI-25                                                                                 ##STR119##                                                                                 ##STR120##                                                                              CH.sub.3                                                                           H                                         VI-26                                                                                 ##STR121##                                                                                 ##STR122##                                                                              CH.sub.3                                                                           H                                         VI-27                                                                                 ##STR123##                                                                                 ##STR124##                                                                              CH.sub.3                                                                           H                                         VI-28                                                                                 ##STR125##                                                                                 ##STR126##                                                                              CH.sub.3                                                                           H                                         VI-29                                                                                 ##STR127##                                                                                 ##STR128##                                                                              CH.sub.3                                                                           H                                         VI-30                                                                                 ##STR129##                                                                                 ##STR130##                                                                              CH.sub.3                                                                           H  136                                    VI-31                                                                                 ##STR131##                                                                                 ##STR132##                                                                              CH.sub.3                                                                           H                                         VI-32                                                                                 ##STR133##                                                                                 ##STR134##                                                                              CH.sub.3                                                                           H                                         VI-33                                                                                 ##STR135##                                                                                 ##STR136##                                                                              CH.sub.3                                                                           H                                         VI-34                                                                                 ##STR137##                                                                                 ##STR138##                                                                              CH.sub.3                                                                           H                                         VI-35                                                                                 ##STR139##                                                                                 ##STR140##                                                                              CH.sub.3                                                                           H                                         VI-36                                                                                 ##STR141##                                                                                 ##STR142##                                                                              CH.sub.3                                                                           H                                         VI-37                                                                                 ##STR143##                                                                                 ##STR144##                                                                              CH.sub.3                                                                           H                                         VI-38                                                                                 ##STR145##                                                                                 ##STR146##                                                                              CH.sub.3                                                                           H                                         VI-39                                                                                 ##STR147##                                                                                 ##STR148##                                                                              CH.sub.3                                                                           H                                         VI-40                                                                                 ##STR149##                                                                                 ##STR150##                                                                              CH.sub.3                                                                           H                                         VI-41                                                                                 ##STR151##                                                                                 ##STR152##                                                                              CH.sub.3                                                                           H                                         VI-42                                                                                 ##STR153##                                                                                 ##STR154##                                                                              CH.sub.3                                                                           H                                         VI-43                                                                                 ##STR155##                                                                                 ##STR156##                                                                              C.sub.2 H.sub.5                                                                    H                                         VI-44                                                                                 ##STR157##                                                                                 ##STR158##                                                                              CH.sub.3                                                                           H                                         VI-45                                                                                 ##STR159##                                                                                 ##STR160##                                                                              CH.sub.3                                                                           H                                         VI-46                                                                                 ##STR161##                                                                                 ##STR162##                                                                              CH.sub.3                                                                           H                                         VI-47                                                                                 ##STR163##                                                                                 ##STR164##                                                                              CH.sub.3                                                                           H                                         VI-48                                                                                 ##STR165##                                                                                 ##STR166##                                                                              CH.sub.3                                                                           H                                         VI-49                                                                                 ##STR167##                                                                                 ##STR168##                                                                              CH.sub.3                                                                           H  133                                    VI-50                                                                                 ##STR169##                                                                                 ##STR170##                                                                              CH.sub.3                                                                           H  150                                    __________________________________________________________________________

EXAMPLES OF THE PREPARATION OF STARTING MATERIALS OF THE FORMULA (VIII):##STR171##

8 g (0.2 mol) of sodium hydroxide--dissolved in 15 ml of water--and 6 ml(0.11 mol) of carbon disulphide are simultaneously added dropwise (fromdifferent dropping funnels) to a solution of 20 g (0.1 mol) of2-chlorobenzenesulphonamide in 80 ml of dimethylformamide at 20° C.After the mixture has been stirred for one hour, 13 ml (0.22 mol) ofmethyl iodide are added dropwise, and the reaction mixture is stirredfor a further hour at 20° C. The product is precipitated by the additionof 500 ml of water, and is isolated by filtering it off under suction.

22.1 g (75% of theory) of N-(2-chloro-benzenesulphonyl) S',S"-dimethylisodithiocarbamate of melting point 112° C. are obtained.

In the same manner, it was possible to prepare the following compound ofthe formula (VIII): ##STR172##

USE EXAMPLES Example A

Pre-emergence test/greenhouse

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Seeds of the test plants are sown in normal soil and, after 24 hours,watered with the preparation of the active compound. It is expedient tokeep constant the amount of water per unit area. The concentration ofthe active compound in the preparation is of no importance, only theamount of active compound applied per unit area being decisive. Afterthree weeks, the degree of damage to the plants is rated in % damage incomparison to the development of the untreated control. The figuresdenote:

0%=no action (like untreated control)

100%=total destruction

In this test, for example, the following compound from the preparationexamples shows an excellent activity: 192, 197, 198, 199, 200, 203, 205,206, 210, 212, 216, 217, 218, 219, 220, 221, 224, 226, 227, 234, 238,240, 244, 246, 259, 263, 264.

Example B

Post-emergence test/greenhouse

Solvent: 5 parts by weight of acetone

Emulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

Test plants which have a height of 5-15 cm are sprayed with thepreparation of the active compound in such a way as to apply theparticular amount of active compound desired per unit area. Theconcentration of the spray liquor is so chosen that the particularamounts of active compound desired are applied in 2,000 l of water/ha.After three weeks, the degree of damage to the plants is rated in %damage in comparison to the development of the untreated control. Thefigures denote:

0%=no action (like untreated control)

100%=total destruction

In this test, for example, the following compounds from the preparationexamples exhibited an excellent activity: 192, 197, 198, 199, 200, 203,205, 206, 210, 212, 216, 217, 218, 219, 220, 221, 224, 226, 227, 234,238, 240, 244, 246, 259, 263, 264.

It is understood that the specification and examples are illustrativebut not limitative of the present invention and that other embodimentswithin the spirit and scope of the invention will suggest themselves tothose skilled in the art.

In the following claims, "plant growth" includes increasing ordecreasing growth or even terminating it altogether as in herbicidalactivity.

What is claimed is:
 1. A guanidine derivative of the formula ##STR173##in which m represents the numbers zero, 1 or 2,R⁵ represents alkylhaving up to 6 carbon atoms which may be substituted by halogen; or R⁵represents further the radical ##STR174## wherein R¹⁶ and R¹⁷ areidentical or different and represent hydrogen, halogen, cyano, nitro, C₁-C₆ -alkyl (which may be substituted by fluorine, chlorine, bromine,cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylaminocarbonyl,di-(C₁ -C₄ -alkyl)-aminocarbonyl, hydroxyl, C₁ -C₄ -alkoxy, formyloxy,C₁ -C₄ -alkyl-carbonyloxy, C₁ -C₄ -alkoxy-carbonyloxy, C₁ -C₄-alkylaminocarbonyloxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl, C₁-C₄ -alkylsulphonyl, di-(C₁ -C₄ -alkyl)-aminosulphonyl, C₃ -C₆-cycloalkyl or phenyl), C₂ -C₆ -alkenyl (which may be substituted byfluorine, chlorine, bromine, cyano, C₁ -C₄ -alkoxy-carbonyl, carboxyl orphenyl), C₁ -C₄ -alkoxy (which may be substituted by fluorine, chlorine,bromine, cyano, carboxyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄ -alkylthio, C₁-C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl), C₃ -C₆ -alkenoxy (whichmay be substituted by fluorine, chlorine, bromine, cyano or C₁ -C₄-alkoxy-carbonyl), C₃ -C₆ -alkinoxy or the radical --S(O)_(p) --R¹⁸,wherein p represents the numbers zero, 1 or 2 and R¹⁸ represents C₁ -C₄-alkyl (which may be substituted by fluorine, chlorine, bromine, cyanoor C₁ -C₄ -alkoxy-carbonyl), C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, C₁ -C₄-alkoxy, C₁ -C₄ -alkylamino or di-(C₁ -C₄ -alkyl)-amino, or R¹⁶ and R¹⁷(which are identical or different) represent phenyl or phenoxy, C₁ -C₄-alkylcarbonylamino, C₁ -C₄ -alkoxy-carbonylamino, C₁ -C₄-alkylamino-carbonylamino, di-(C₁ -C₄ -alkyl)-amino-carbonylamino or theradical --CO--R¹⁹, wherein R¹⁹ represents C₁ -C₆ -alkyl, C₁ -C₆ -alkoxy,C₃ -C₆ -alkenoxy, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylamino or di-(C₁ -C₄-alkyl)-amino (which may be substituted by fluorine and/or chlorine) orR¹⁶ and R¹⁷ (which are identical or different) represent C₁ -C₄-alkylsulphonyloxy, di-(C₁ -C₄ -alkyl)-aminosulphonylamino or theradical --CH═N--R²⁰, wherein R²⁰ represents C₁ -C₆ -alkyl (which may besubstituted by fluorine, chlorine, cyano, carboxyl, C₁ -C₄-alkoxy-carbonyl, C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄-alkylsulphonyl), benzyl (which may be substituted by fluorine orchlorine), C₃ -C₆ -alkenyl or C₃ -C₆ -alkinyl (which may be substitutedby fluorine or chlorine), phenyl (which may be substituted by fluorine,chlorine, bromine, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, trifluoromethyl,trifluoromethoxy or trifluoromethylthio), C₃ -C₆ -alkenoxy, C₃ -C₆-alkinoxy, benzyloxy or C₁ -C₆ -alkoxy (which may be substituted byfluorine and/or chlorine), or R¹⁶ and R¹⁷ (which are identical ordifferent) represent amino, C₁ -C₄ -alkylamino, di-(C₁ -C₄-alkyl)-amino, phenylamino, C₁ -C₄ -alkyl-carbonylamino, C₁ -C₄-alkoxycarbonylamino, C₁ -C₄ -alkyl-sulphonylamino, orphenylsulphonylamino (which may be substituted by fluorine, chlorine,bromine or methyl); R⁵ represents further the radical ##STR175## whereinR²¹ represents hydrogen or C₁ -C₃ -alkyl and R²² and R²³ are identicalor different and represent hydrogen, fluorine, chlorine, bromine, nitro,cynao, C₁ -C₄ -alkyl (which may be substituted by fluorine and/orchlorine), C₁ -C₄ -alkoxy (which may be substituted by fluorine and/orchlorine), carboxyl, C₁ -C₄ -alkoxycarbonyl, C₁ -C₄ -alkylsulphonyl ordi-(C₁ -C₄ -alkyl)-aminosulphonyl; R⁵ represent further the radical##STR176## wherein R²⁴ and R²⁵ are identical or different and representhydrogen, fluorine, chlorine, bromine, nitro, cyano, C₁ -C₄ -alkyl(which may be substituted by fluorine and/or chlorine) or C₁ -C₄ -alkoxy(which may be substituted by fluorine and/or chlorine); R⁵ representsfurther the radical ##STR177## wherein R²⁶ and R²⁷ are identical ordifferent and represent hydrogen, fluorine, chlorine, bromine, nitro,cyano, C₁ -C₄ -alkyl (which may be substituted by fluorine and/orchlorine), C₁ -C₄ -alkoxy (which may be substituted by fluorine and/orchlorine), C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄-alkylsulphonyl (which may be substituted by fluorine and/or chlorine),and di-(C₁ -C₄ -alkyl)-aminosulphonyl or C₁ -C₄ -alkoxy-carbonyl; R⁵represents further the radical ##STR178## wherein R²⁸ and R²⁹ areidentical or different and represent hydrogen, fluorine, chlorine,bromine, C₁ -C₄ -alkyl (which may be substituted by fluorine and/orbromine), C₁ -C₄ -alkoxy (which may be substituted by fluorine and/orchlorine), C₁ -C₄ -alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄-alkylsulphonyl (which may be substituted by fluorine and/or chlorine)or di-(C₁ -C₄ -alkyl)-aminosulphonyl; or R⁵ represents further theradical ##STR179## wherein R³⁰ and R³¹ are identical or different andrepresent hydrogen, fluorine, chlorine, bromine, cyano, nitro, C₁ -C₄-alkyl (which may be substituted by fluorine and/or chlorine), C₁ -C₄-alkoxy (which may be substituted by fluorine and/or chlorine), C₁ -C₄-alkylthio, C₁ -C₄ -alkylsulphinyl or C₁ -C₄ -alkylsulphonyl which maybe substituted by fluorine and/or chlorine), di-(C₁ -C₄-alkyl)-aminosulphonyl or C₁ -C₄ -alkoxy-carbonyl, Z represents oxygen,sulphur or the grouping N--Z¹,wherein Z¹ represents hydrogen, C₁ -C₄-alkyl (which may be substituted by fluorine, chlorine, bromine orcyano), C₃ -C₆ -cycloalkyl, benzyl, phenyl (which may be substituted byfluorine, chlorine, bromine or nitro), C₁ -C₄ -alkylcarbonyl, C₁ -C₄-alkoxy-carbonyl or di-(C₁ -C₄ -alkyl)-aminocarbonyl, R² represents apyrimidin-2-yl radical which is substituted by halogen, amino, cyano orformyl and/or by C₁ -C₃ -alkyl (which may be substituted by fluorineand/or chlorine), C₁ -C₃ -alkoxy (which may be substituted by fluorineand/or chlorine), C₁ -C₃ -alkylamino, di-C₁ -C₃ -)-alkylamino, C₁ -C₃-alkylcarbonyl or C₁ -C₃ -alkoxy-carbonyl, R³ represents hydrogen, C₁-C₄ -alkyl (which is optionally substituted by fluorine, chlorine,bromine, cyano, hydroxyl or C₁ -C₂ -alkoxy), C₃ -C₆ -cycloalkyl, C₃ -C₆-alkenyl, C₃ -C₆ -alkinyl, or benzyl (which is optionally substituted byfluorine, chlorine or methyl), R⁹ represents hydrogen or C₁ -C₄ -alkyland R¹⁰ represents C₁ -C₄ -alkyl (which is optionally substituted byfluorine, chlorine, bromine, cyano, C₁ -C₄ -alkoxy or C₁ -C₄-alkoxy-carbonyl), C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl, C₃ -C₆ -cycloalkyl(which is optionally interrupted by a --SO₂ bridge), benzyl orphenylethyl (which are optionally substituted by fluorine, chlorine ormethyl), phenyl (which is optionally substituted by fluorine, chlorine,bromine, nitro, cyano, C₁ -C₄ -alkyl, trifluoromethyl, C₁ -C₄ -alkoxy,trifluoromethoxy, C₁ -C₄ -alkylthio or trifluoromethylthio), pyrimidyl,C₁ -C₄ -alkyl-carbonyl, benzoyl, C₁ -C₄ -alkoxy-carbonyl, C₁ -C₄-alkylsulphonyl or phenylsulphonyl (which is optionally substituted byfluorine, chlorine, bromine or methyl), or R⁹ and R¹⁰ togetherrepresents C₄ -C₆ -alkanediyl which is optionally interrupted by anoxygen atom; and M represents hydrogen, one equivalent of a metal, or anammonium radical which is optionally substituted by C₁ -C₆ -alkyl (whichis optionally substituted by chlorine), C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyland/or benzyl (which is optionally substituted by fluorine, chlorine ormethyl), alkyl, alkenyl, alkinyl and/or aralkyl, or--in the case inwhich M is bonded to the same nitrogen atom as R² --also representsC₁-C₆ -alkyl (which is optionally substituted by fluorine, chlorine, orcyano), C₃ -C₆ -alkenyl, C₃ -C₆ -alkinyl or benzyl, or an acid adductthereof.
 2. A compound or adduct according to claim 1, in whichMrepresents the number 2, R³ represents hydrogen or methyl, R⁹ representshydrogen or methyl, R¹⁰ represents hydrogen, C₁ -C₄ -alkyl (which may besubstituted by fluorine and/or chlorine), cyclohexyl, phenyl (which maybe substituted by fluorine, chlorine, bromine, methyl and/ortrifluoromethyl), benzyl, pyrimidinyl, C₁ -C₄ -alkyl-carbonyl, C₁ -C₄-alkoxy-carbonyl, C₁ -C₄ -alkyl-sulphonyl or phenylsulphonyl (which maybe substituted by fluorine, chlorine, bromine or methyl) and Mrepresents hydrogen, sodium, potassium or one equivalent of magnesium orcalcium.
 3. A 1:1 acid adduct according to claim 1, with an acidselected from the group consisting of hydrogen fluoride, hydrogenchloride, hydrogen bromide, hydrogen iodide, sulphuric acid, phosphoricacid, an alkanesulphonic acid having up to 4 carbon atoms and optionallysubstituted by fluorine or chlorine, or a benzene- ornaphthalene-sulphonic acid which is optionally substituted by fluorine,chlorine or methyl.
 4. A compound according to claim 1, in whichmrepresents the number 2, R² represents the radical ##STR180## whereinR³⁷ represents hydrogen, methyl or methoxy, R³⁸ represents hydrogen,chlorine, methyl, acetyl or methoxycarbonyl and R³⁹ represents C₁ -C₄-alkyl or C₁ -C₄ -alkoxy, R³ represents hydrogen or methyl, R⁵represents the radical ##STR181## R⁹ represents hydrogen or methyl andR¹⁰ represents C₁ -C₃ -alkyl, phenyl, acetyl, methoxycarbonyl,phenylsulphonyl or p-toluenesulphonyl; M represents hydrogen, sodium,potassium or one equivalent of magnesium or calcium; and R¹⁶ representsfluorine, chlorine, bromine, methyl, trifuoromethyl, C₁ -C₂ -alkoxy,difluoromethyl, trifluoromethoxy, phenyl or C₁ -C₂ -alkoxycarbonyl andR¹⁷ represents hydrogen;or in which R¹⁶ and R¹⁷ represent hydrogen orR¹⁶ represents chlorine, nitro, methyl, trifluoromethyl or methoxy andR¹⁷ represents fluorine, chlorine, bromine, methyl, trifluoromethyl,cyano, nitro or methoxy;or in which R¹⁶ represents hydrogen, fluorine,chlorine, bromine, nitro, methyl, trifluoromethyl, C₁ -C₂ -alkoxy,difluoromethoxy, trifluoromethoxy, phenyl or C₁ -C₂ -alkoxy-carbonyl andR¹⁷ represents hydrogen, fluorine, chlorine, bromine, nitro, methyl,trifluoromethyl, C₁ -Chd 2-alkoxy, difluoromethoxy or trifluoromethoxy.5. A compound according to claim 1 of the formula ##STR182##
 6. Acompound according to claim 1 of the formula ##STR183##
 7. A compoundaccordng to claim 1 of the formula ##STR184##
 8. A compound according toclaim 1 of the formula ##STR185##
 9. A compound according to claim 1 ofthe formula ##STR186##
 10. A compound according to claim 1 of theformula ##STR187##
 11. A compound according to claim 1 of the formula##STR188##
 12. A compound according to claim 1 of the formula ##STR189##13. A compound according to claim 1 of the formula ##STR190##
 14. Aplant growth regulating composition comprising a herbicidally or plantgrowth regulating effective amount of a compound or adduct according toclaim 1 in admixture with a diluent.
 15. A method of controlling thegrowth of plants which comprises administering to such plants or to ahabitat in which they are grown a plant growth regulating effectiveamount of a compound or adduct according to claim
 1. 16. The methodaccording to claim 15, wherein such compound is ##STR191##